WO2016052663A1 - Laminate sheet and foam laminate sheet, and production method and application method for same - Google Patents

Laminate sheet and foam laminate sheet, and production method and application method for same Download PDF

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Publication number
WO2016052663A1
WO2016052663A1 PCT/JP2015/077850 JP2015077850W WO2016052663A1 WO 2016052663 A1 WO2016052663 A1 WO 2016052663A1 JP 2015077850 W JP2015077850 W JP 2015077850W WO 2016052663 A1 WO2016052663 A1 WO 2016052663A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
laminated sheet
foaming agent
layer
foamed
Prior art date
Application number
PCT/JP2015/077850
Other languages
French (fr)
Japanese (ja)
Inventor
義昭 根津
Original Assignee
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to RU2017114493A priority Critical patent/RU2684368C2/en
Priority to JP2016552146A priority patent/JP6642441B2/en
Priority to CN201580053099.4A priority patent/CN106794663A/en
Priority to EP15847938.6A priority patent/EP3202566B1/en
Priority to KR1020177004650A priority patent/KR20170062444A/en
Publication of WO2016052663A1 publication Critical patent/WO2016052663A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B32B27/205—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents the fillers creating voids or cavities, e.g. by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/007—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0242—Acrylic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability

Definitions

  • the present invention relates to a laminate sheet, a foam laminate sheet, and a production method and a construction method thereof.
  • the foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like.
  • the laminated sheet means a state before foaming of the foamed laminated sheet (so-called unfoamed raw fabric) or a sheet useful as various decorative materials in a state where no foamed resin layer is provided.
  • a decorative material such as wallpaper is applied by combining a backing paper mixed with a pulp component and a synthetic resin component and a methylcellulose-based adhesive.
  • a wallpaper having a laminated structure of paper and a decorative layer, and when the wallpaper is applied to a wall surface using an adhesive, peeling of the wallpaper from the wall surface is peeled off by the adhesive layer, and the adhesive Is a methylcellulose-based adhesive having a peeling strength of 100 to 500 g / 3 cm from the wall surface of the wallpaper, and the backing paper is a mixture of a pulp component and a synthetic resin component, and delamination of the backing paper Wallpapers characterized in that the strength is greater than the peel strength of the wallpaper from the wall surface.
  • the backing paper which is a mixture of the above pulp component and synthetic resin component, is bonded to the wall surface, which is the construction surface, using the small dimensional change when wet (low elongation in water) unique to synthetic fiber mixed paper. It is possible to apply the agent and then to construct a wallpaper having the backing paper. There is an advantage that even an ordinary consumer can easily apply an adhesive to a work surface. In addition, by combining the methylcellulose adhesive and the backing paper, when replacing the old wallpaper, it can be peeled off between the backing paper and the adhesive, and the paper remaining on the construction surface or the coated paper can be removed. There is a merit that there is little damage to the construction surface and there is little influence on the newly stuck wallpaper.
  • a starch adhesive starch paste, starch paste with a synthetic resin added
  • a methylcellulose adhesive is generally used in addition to a methylcellulose adhesive.
  • starch adhesive starch paste, starch paste with a synthetic resin added
  • the adhesive strength between the backing paper and the adhesive is too strong, and when replacing an old wallpaper, separation between papers may occur, and the backing paper may remain on the construction surface or damage the construction surface.
  • wallpaper can be easily applied after the adhesive is applied to the work surface, and the backing is used when replacing old wallpaper. It is desired to peel between the paper and the adhesive.
  • An object of the present invention is to provide a novel laminated sheet and a foamed laminated sheet (collectively referred to as “wallpaper or the like”), and more specifically, in addition to a combination of a synthetic fiber mixed paper and a methylcellulose-based adhesive.
  • An object of the present invention is to provide a wallpaper or the like that can be easily applied after the adhesive is applied to the construction surface and that can be peeled off between the backing paper and the adhesive when the adhesive is replaced.
  • the present invention relates to the following laminated sheets, foamed laminated sheets, and methods for producing them.
  • the resin layer is an olefin resin layer.
  • the resin layer is a foaming agent-containing resin layer or a layer composed of a laminate including the foaming agent-containing resin layer.
  • the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides. 5.
  • the resin layer is a foaming agent-containing resin layer, or a layer composed of a laminate including a foaming agent-containing resin layer, and the ionizing radiation is an electron beam.
  • Item 9 The method for producing a laminated sheet according to Item 7 or 8, wherein the crosslinking of the radiation crosslinking material and the resin crosslinking of the foaming agent-containing resin layer are simultaneously performed.
  • the manufacturing method of the foaming lamination sheet which foams the said foaming agent containing resin layer by heating.
  • a construction method comprising sticking the laminated sheet or foam laminated sheet according to any one of the above items 1 to 6 to a work surface coated with an adhesive.
  • a construction method characterized in that an adhesive is applied to the back side of the laminated sheet or foamed laminated sheet according to any one of items 1 to 6 and then adhered to the construction surface.
  • the fibrous base material contains a cross-linked product of an ionizing radiation cross-linkable material. (Dimensional change) is suppressed to a minimum. Therefore, it can be easily applied after the adhesive is applied to the work surface, and can be peeled off between the fibrous base material and the adhesive when reattaching regardless of the type of adhesive. .
  • This effect can be obtained by both the laminated sheet and the foamed laminated sheet of the present invention.
  • Such a laminated sheet and foamed laminated sheet of the present invention have a great advantage in that general consumers can easily construct (stick) and replace them.
  • the laminated sheet of the present invention is a laminated sheet in which at least a resin layer is laminated on a fibrous base material, and the fibrous base material contains a cross-linked product of an ionizing radiation cross-linkable material.
  • the laminated sheet of the present invention having the above characteristics contains the cross-linked product regardless of the type of the fiber material of the fibrous base material because the fibrous base material contains a cross-linked product of the ionizing radiation cross-linking material.
  • the underwater elongation (dimensional change) is suppressed to a minimum. Therefore, it can be easily applied after the adhesive is applied to the work surface, and can be peeled off between the fibrous base material and the adhesive when reattaching regardless of the type of adhesive. .
  • This effect can be obtained by both the laminated sheet and the foamed laminated sheet of the present invention.
  • Such a laminated sheet and foamed laminated sheet of the present invention have a great advantage in that general consumers can easily construct (stick) and replace them.
  • the direction in which the resin layer is laminated as viewed from the fibrous base material is referred to as “upper” or “front surface”, and the resin layer is laminated from the fibrous base material.
  • the side opposite to the direction is referred to as “down” or “back surface”.
  • Fibrous base material As the fibrous base material, one containing a cross-linked product of ionizing radiation cross-linking material is used.
  • the cross-linked product of the ionizing radiation cross-linking material is impregnated with the ionizing radiation cross-linking material in a fibrous base material (one in a fibrous sheet) (impregnation includes various modes such as dipping, coating, spraying, etc.). It is formed by irradiating with ionizing radiation.
  • the fibrous sheet examples include wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet such as guanidine sulfamate, guanidine phosphate, etc. Treated with flame retardant); inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; synthetic fiber mixed paper (paper made by mixing pulp and synthetic fiber), etc. Is mentioned.
  • wallpaper general paper pulp-based sheet sized with a known sizing agent
  • flame-retardant paper pulp-based sheet such as guanidine sulfamate, guanidine phosphate, etc. Treated with flame retardant
  • inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide
  • fine paper fine paper
  • thin paper thin paper
  • synthetic fiber mixed paper paper made by mixing pulp and synthetic fiber
  • the fibrous sheet used in the present invention includes those that fall under the category of nonwoven fabric.
  • the basis weight of the fibrous sheet is not critical, preferably about 50 ⁇ 300g / m 2, more preferably about 50 ⁇ 130g / m 2.
  • the ionizing radiation crosslinkable material is not particularly limited, and a prepolymer containing in the molecule a radical polymerizable unsaturated group or a cationic polymerizable functional group capable of performing a crosslinking reaction (polymerization crosslinking reaction) by irradiation with ionizing radiation such as ultraviolet rays and electron beams.
  • a crosslinking reaction polymerization crosslinking reaction
  • ionizing radiation such as ultraviolet rays and electron beams.
  • Polymers including oligomers
  • monomers having a relatively low viscosity are preferred in consideration of permeability to the fibrous base material.
  • a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group.
  • a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable.
  • the (meth) acryloyl group means an acryloyl group or a methacryloyl group.
  • Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.
  • Examples of the monomer having a radical polymerizable unsaturated group include, as monofunctional monomers, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
  • Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide tri (meth) acrylate.
  • Dipentaerythritol tetra (meth) acrylate dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
  • Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers.
  • Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.
  • Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.
  • the ionizing radiation crosslinking material it is preferable to use a polyfunctional prepolymer or a polyfunctional monomer having two or more polymerizable functional groups in one molecule as these prepolymers or monomers in order to promote a crosslinking reaction. .
  • the ionizing radiation crosslinking material a material obtained by combining these prepolymers or monomers with other materials may be used.
  • materials used in combination with these prepolymers or monomers include resins such as acrylic resins, urethane resins, epoxy resins, and polyester resins that are commonly used as general paints.
  • the prepolymers or monomers may function as a crosslinking agent that crosslinks these resins.
  • the ionizing radiation used for cross-linking the ionizing radiation cross-linking material electromagnetic waves or charged particles having energy capable of cross-linking the molecules in the ionizing radiation cross-linking material are used.
  • electromagnetic waves or charged particles having energy capable of cross-linking the molecules in the ionizing radiation cross-linking material are used.
  • ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.
  • the ultraviolet light source for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used.
  • the wavelength of ultraviolet light is usually preferably 190 to 380 nm.
  • various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.
  • those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.
  • the density of the fibrous base material containing a crosslinked product of an ionizing radiation crosslinked materials differs by content type and cross-linking of the fibrous base material before containing crosslinked product, basis weight of 65 g / m 2 of about
  • the density of the fiber base material containing the cross-linked product is about 0.60 to 0.65 g / cm 3
  • the inorganic paper containing an inorganic additive such as aluminum hydroxide is used. Is about 1.0 g / cm 3 .
  • the inter-paper strength of the fibrous base material containing the crosslinked product is about 0.25 to 3.8 N / (3 cm width) when a fibrous sheet having a basis weight of about 65 g / m 2 is used.
  • Resin layer In the laminated sheet of the present invention, at least a resin layer is laminated on a fibrous base material.
  • This resin layer can be formed by a known film forming method such as a T-die film forming method or a calendar film forming method.
  • vinyl chloride resins and olefin resins conventionally used for wall covering materials can be widely used.
  • the vinyl chloride resin may cause the plasticizer to bleed over time. Therefore, from the viewpoint of enhancing the durability of the laminated sheet, an olefin resin is preferable to a vinyl chloride resin, and specifically, an ethylene resin is preferably contained.
  • ethylene-based resin examples include not only polyethylene (PE) but also ethylene copolymers having monomers other than ethylene and ethylene (hereinafter, abbreviated as “ethylene copolymers”).
  • low density polyethylene LDPE
  • medium density polyethylene MDPE
  • high density polyethylene HDPE
  • linear low density polyethylene LLDPE
  • Ethylene copolymer is suitable for extrusion film formation from the viewpoint of melting point and MFR.
  • the ethylene copolymer include an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-acrylic acid copolymer (EAA), and an ethylene-ethyl acrylate copolymer ( EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene- ⁇ olefin copolymer, and the like.
  • EVA ethylene-vinyl acetate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EAA ethylene-acrylic acid copolymer
  • EEA ethylene-ethyl acrylate copolymer
  • EMA ethylene-methyl acrylate copolymer
  • EEMAA ethylene-methacrylic acid copolymer
  • ethylene-vinyl acetate copolymer and ethylene-methyl methacrylate copolymer are particularly preferred.
  • ethylene -The content of vinyl acetate copolymer and ethylene-methyl methacrylate copolymer is preferably 70% by weight or more, and more preferably 80% by weight or more.
  • the content of monomers other than ethylene is preferably 5 to 25% by weight, more preferably 9 to 20% by weight.
  • the ethylene-vinyl acetate copolymer has a vinyl acetate copolymerization ratio (VA amount) of preferably 9 to 25% by weight, more preferably 9 to 20% by weight.
  • VA amount vinyl acetate copolymerization ratio
  • the ethylene-methyl methacrylate copolymer has a methyl methacrylate copolymerization ratio (MMA amount) of preferably 5 to 25% by weight, more preferably 5 to 15% by weight.
  • the ethylene-methacrylic acid copolymer preferably has a copolymerization ratio (MAA amount) of acrylic acid of 2 to 15% by mass, more preferably 5 to 11% by mass.
  • the resin component contained in the resin layer has an MFR (melt flow rate) of 10 to 40 g measured at 190 ° C. and a load of 21.18 N described in JIS K-6922, depending on the film forming method. / 10 minutes is preferred.
  • MFR melt flow rate
  • the temperature rise when forming the resin layer by extrusion film formation is small, and the film can be formed in a non-foamed state.
  • the printing process can be performed, and there are few missing patterns. If the MFR is too large, the resin is too soft and the resulting resin layer may have insufficient scratch resistance.
  • the resin layer may be a foaming agent-containing resin layer or a layer formed of a laminate including the foaming agent-containing resin layer.
  • the obtained laminated sheet means a so-called original fabric having a foaming agent-containing resin layer.
  • the foaming lamination sheet of this invention is obtained by making a foaming agent containing resin layer foam.
  • the resin composition for forming the foaming agent-containing resin layer for example, a resin composition containing the above resin component, inorganic filler, pigment, pyrolytic foaming agent, foaming aid, crosslinking aid and the like can be suitably used. .
  • stabilizers, lubricants and the like can be used as additives.
  • thermally decomposable foaming agent examples include azo series such as azodicarbonamide (ADCA) and azobisformamide; hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide.
  • the content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 7 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.
  • the foaming aid is preferably a metal oxide and / or a fatty acid metal salt.
  • a metal oxide and / or a fatty acid metal salt For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, laurin
  • Magnesium acid, zinc oxide, magnesium oxide and the like can be used.
  • the content of these foaming auxiliaries is preferably about 0.3 to 10 parts by mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the resin component.
  • the effect of the foaming aid is impaired by the reaction between the acrylic acid part of EMAA and the metallic foaming aid in the foaming process.
  • EMAA and ADCA foaming agent it is preferable to use a carboxylic acid hydrazide compound as a foaming aid as described in JP-A-2009-197219.
  • the carboxylic acid hydrazide compound is preferably used in an amount of about 0.2 to 1 part by mass with respect to 1 part by mass of the ADCA foaming agent.
  • Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound.
  • the content of the inorganic filler is preferably about 0 to 100 parts by mass and more preferably about 20 to 70 parts by mass with respect to 100 parts by mass of the resin component.
  • pigments for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve) ), Cadmium red, ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide.
  • organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone.
  • the content of the pigment is preferably about 10 to 50 parts by mass, more preferably about 15 to 30 parts by mass with respect to 100 parts by mass of the resin component.
  • the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. What is necessary is just to implement according to the method described in the postscript manufacturing method as a method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam.
  • the ionizing radiation applied to the fibrous base material is an electron beam
  • crosslinking of the ionizing radiation-crosslinking material and resin crosslinking of the foaming agent-containing resin layer can be performed simultaneously.
  • the resin layer may be a resin layer that forms a pattern separately from the pattern layer described later.
  • the pigments and resins used are the same as those that can be used in the pattern layer described later.
  • the resin layer may be a resin layer made of an ionizing radiation curable resin, a thermosetting resin (including a room temperature curable resin, a two-component reaction curable resin), or the like.
  • the thickness of the resin layer (including both single layer and multilayer) is preferably about 40 to 200 ⁇ m, and the resin layer is a foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer.
  • the thickness of the resin layer after foaming is preferably about 300 to 1000 ⁇ m.
  • Non-foamed resin layers A and B The foaming agent-containing resin layer may have a non-foamed resin layer on one side or both sides.
  • the back surface (surface on which the fibrous base material is laminated) of the foaming agent-containing resin layer has a non-foamed resin layer B (adhesive resin layer) for the purpose of improving the adhesive strength with the fibrous base material. Also good.
  • the resin component of the adhesive resin layer is not particularly limited, but ethylene-vinyl acetate copolymer (EVA) is preferable.
  • EVA ethylene-vinyl acetate copolymer
  • the vinyl acetate component (VA component) is preferably 10 to 46% by mass, more preferably 15 to 41% by mass.
  • the thickness of the adhesive resin layer is not limited, but is preferably about 3 to 50 ⁇ m, more preferably about 5 to 20 ⁇ m.
  • the non-foamed resin layer A may be formed on the upper surface of the foaming agent-containing resin layer for the purpose of clarifying the pattern when the pattern layer is formed or improving the scratch resistance of the foamed resin layer.
  • Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluorine resins, and the like, among which polyolefin resins are preferable.
  • polyolefin resins examples include polyethylene (low density polyethylene (LDPE) or high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, and ethylene and ⁇ -olefins having 4 or more carbon atoms.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • polypropylene polypropylene
  • polybutene polybutadiene
  • polyisoprene polyisoprene
  • other resins examples include ethylene and ⁇ -olefins having 4 or more carbon atoms.
  • Polymers linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer and other ethylene ( Examples thereof include at least one of a (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer (EVA), an ethylene-vinyl acetate copolymer saponified product, an ethylene-vinyl alcohol copolymer, and an ionomer.
  • LLDPE linear low density polyethylene
  • EVA ethylene-vinyl acetate copolymer
  • EVA ethylene-vinyl acetate copolymer saponified product
  • an ethylene-vinyl alcohol copolymer ethylene-vinyl alcohol copolymer
  • ionomer ionomer
  • the non-foamed resin layer A (particularly an ethylene-vinyl alcohol copolymer layer) is used.
  • (meth) acrylic acid means acrylic acid or methacrylic acid, and the same applies to other parts described as (meth).
  • the thickness of the non-foamed resin layer A is not limited, but is preferably about 2 to 50 ⁇ m, more preferably about 5 to 20 ⁇ m.
  • a pattern pattern layer may be formed on a resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.) or a primer layer described later, if necessary.
  • the design pattern layer imparts design properties to the laminated sheet and the foamed laminated sheet.
  • Examples of the design pattern include a grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, an abstract pattern, a flower pattern, etc. You can choose according to your purpose.
  • the pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like.
  • a printing ink containing a colorant, a binder resin, and a solvent can be used as the printing ink. These inks may be known or commercially available.
  • a pigment used in the foaming agent-containing resin layer can be used as appropriate.
  • the binder resin can be set according to the type of base on which the pattern layer is formed.
  • acrylic resin styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.
  • the solvent examples include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane
  • the thickness of the pattern layer varies depending on the type of pattern, but is generally preferably about 0.1 to 10 ⁇ m.
  • a primer layer may be formed as necessary on the primer layer resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.) or the pattern layer.
  • acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used.
  • acrylic, chlorinated polypropylene, etc. Is desirable.
  • the acryl examples include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylate methyl- (meth) acrylic acid (Meth) such as butyl copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester may be mentioned.
  • Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).
  • polystyrene resin one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.
  • polyisocyanate having two or more isocyanate groups in the molecule is used.
  • aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate ) Isocyanates are used.
  • the thickness of the primer layer is not limited, but is preferably about 0.1 to 10 ⁇ m, more preferably about 0.1 to 5 ⁇ m.
  • Pattern layer or primer layer has a surface protective layer intended for gloss adjustment and / or pattern layer protection May be.
  • the type of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed.
  • the ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.
  • An embossed pattern may be provided on the front surface of the embossed laminated sheet or the foamed laminated sheet. In this case, what is necessary is just to emboss from the uppermost surface layer (opposite side to the fibrous sheet). Embossing can be performed by known means such as pressing an embossed plate.
  • a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a sand texture, a hairline, a geometric pattern, a multi-row groove, and a contour pattern.
  • the foamed laminated sheet of the present invention can be obtained by foaming the foaming agent-containing resin layer of the laminated sheet.
  • the manufacturing method of the laminated sheet of the present invention is not limited, for example, (1) forming at least a resin layer on the fibrous base material; (2) impregnating the fibrous base material with an ionizing radiation cross-linking material, After passing through the above-mentioned two steps, at least the fibrous base material is irradiated with ionizing radiation, and the ionized radiation cross-linking material is cross-linked to form a cross-linked product. .
  • a step of forming a resin layer on a fibrous base material including both a crosslinked material and a fibrous sheet), and a fibrous substrate (crosslinked material)
  • the resin layer is preferably formed by extrusion film formation.
  • the order of performing the steps (1) and (2) is not limited, but when the resin layer is formed by extrusion film formation, the resin layer is laminated on the fibrous base material with good adhesion. From the viewpoint, it is preferable to perform the step (2) after performing the step (1).
  • the method of impregnating the fibrous base material with the ionizing radiation cross-linking material in the step (2) is not particularly limited, but the resin layer is formed on the fibrous base material (if the step (1) is performed first)
  • a method of coating the ionizing radiation crosslinkable material on the opposite side of the formed surface a method of immersing the fibrous base material in the ionizing radiation crosslinkable material, and the like.
  • the ionizing radiation cross-linking material may be diluted with a solvent as necessary.
  • the resin layer is a layer composed of a laminate including a foaming agent-containing resin layer and has a non-foaming resin layer on one or both sides of the foaming agent-containing resin layer, the non-foaming resin layer B and / or non-foaming
  • the resin layer A may be formed by extrusion film formation or may be formed by heat laminating each film, but simultaneous extrusion film formation by a T-die extruder is suitable.
  • a multi-manifold type T die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers can be used.
  • an extrusion port (so-called die) of the extruder is used.
  • Inorganic filler residues (so-called eyes and eyes) are easily generated, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic filler is included in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above. That is, it is possible to suppress the occurrence of the above-mentioned corners by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers.
  • electron beam irradiation may be performed.
  • the resin component can be cross-linked to adjust the surface strength, foaming characteristics, etc. of the foamed resin layer.
  • the energy of the electron beam is preferably about 150 to 250 kV, more preferably about 175 to 200 kV.
  • the irradiation dose is preferably about 10 to 100 kGy, more preferably about 10 to 50 kGy.
  • a known electron beam irradiation apparatus can be used as the electron beam source.
  • crosslinking of the ionizing radiation crosslinking material and resin crosslinking of the foaming agent-containing resin layer can be performed simultaneously.
  • a pattern layer and a primer layer are formed in any order, and if necessary, a surface protective layer is formed to form a laminated sheet, and then heat-treated.
  • a foaming laminated sheet is obtained by making the foaming agent-containing resin layer into a foamed resin layer.
  • Fig. 1 illustrates the layer structure of a laminated sheet in which a non-foamed resin layer B, a foaming agent-containing resin layer, a non-foamed resin layer A, a pattern pattern layer, a primer layer, and a surface protective layer are sequentially formed on a fibrous base material. To do.
  • Each of these layers can be laminated by combining coating such as printing and coating, extrusion film formation and the like, and coating such as printing and coating can be performed according to a conventional method.
  • the heat treatment conditions may be any conditions as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent.
  • the heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 25 to 80 seconds.
  • an embossed pattern is added, it is carried out by a known means such as pressing an embossed plate.
  • the laminated sheet and the foamed laminated sheet of the present invention can be constructed by applying an adhesive to the construction surface and then sticking it to the construction surface.
  • the construction surface to which the laminated sheet and the foamed laminated sheet of the present invention are applied is not particularly limited, and various uses that require decoration can be applied, and examples of the construction surface include a wall surface and / or a ceiling. That is, the laminated sheet and the foamed laminated sheet of the present invention are particularly useful as wallpaper and / or ceiling material.
  • the adhesive used for the construction of the laminated sheet and the foamed laminated sheet of the present invention is not particularly limited, and conventional adhesives such as starch adhesives (starch glue, starch paste with a synthetic resin added, etc.), methylcellulose adhesives, etc.
  • the adhesive can be selected and used according to the type of the work surface.
  • the laminated sheet and the foamed laminated sheet of the present invention are adhesives other than methylcellulose-based adhesives, for example, when applied using a starch-based adhesive generally used in the construction of wallpaper and ceiling materials, It is possible to peel between the fibrous base material and the adhesive at the time of replacement, and it is difficult for the fibrous base material to remain on the work surface, so that replacement is easy.
  • the construction method of the laminated sheet and the foamed laminated sheet of the present invention is not limited to the construction method described above, and after applying the adhesive to the back side of the laminated sheet and the foamed laminated sheet (the back side of the fibrous base material), It is also possible to construct by a general method of sticking to the construction surface.
  • Example 1 Using a three-type, three-layer multi-manifold T-die extruder, i) non-foamed resin layer B, ii) foaming agent-containing resin layer, and iii) non-foamed resin layer A in this order were 7 ⁇ m, 70 ⁇ m, and 7 ⁇ m thick. Filmed.
  • the extrusion conditions were as follows: the i) layer resin had a cylinder temperature of 100 ° C., the ii) layer resin composition had a cylinder temperature of 120 ° C., and the iii) layer resin had a cylinder temperature of 130 ° C. The die temperatures were all 120 ° C.
  • the surface of i) layer is laminated on plain paper backing paper (WK-665DO, KJ special paper) heated to a surface temperature of 120 ° C. "Shin Nakamura Chemical" was impregnated by coating from the backing paper side.
  • the above iii) layer is irradiated with an electron beam (200 KV, 30 kGy) to crosslink the impregnated ionizing radiation cross-linked material, and at least the foaming agent-containing resin layer ii) is cross-linked to form a laminated sheet. Produced.
  • the EVA-based aqueous emulsion was 2 g / m 2 coating as a primer treatment by a gravure printing machine, thereon picture water based ink ( "Hyde Rick” Dainichiseika Color & Chemicals Mfg. Co., Ltd.), the protective layer water based ink ( Using “ALTOP” (manufactured by Dainichi Seika Kogyo Co., Ltd.), a texture pattern was printed by a gravure printing machine to form a pattern layer, and then a protective layer was formed.
  • a laminated sheet (non-foamed) having a fibrous base material layer (plain paper backing paper), a non-foamed resin layer B, a foaming agent-containing resin layer, a non-foamed resin layer A, a primer layer, a pattern layer and a protective layer in this order.
  • the original fabric was obtained.
  • the foaming agent contained in the foaming agent-containing resin layer was foamed by heating in a gear oven (220 ° C. ⁇ 30 seconds). Furthermore, the embossed texture pattern was applied to the foam from the outermost surface to prepare a foamed laminated sheet (foamed wallpaper).
  • foaming agent“ Vinihole AC # 3, manufactured by Eiwa Kasei Kogyo ”4 parts by weight, foaming aid“ Fco Chem ZNS-P ADEKA ”4 parts by weight, crosslinking aid“ OPSTAR ” "JUA-702, made by JSR” was formed from a resin composition containing 1 part by weight.
  • the non-foamed resin layer A was formed from an ethylene-methacrylic acid copolymer resin “Nucleel N1560, manufactured by Mitsui DuPont Polychemical”.
  • Comparative Example 1 A laminated sheet and a foamed laminated sheet were produced in the same manner as in Example 1 except that the backing paper was not impregnated with the ionizing radiation cross-linking material.
  • Comparative Example 2 A laminated sheet and a foamed laminated sheet were prepared in the same manner as in Example 1 except that fleece paper (made by Ahlstrom), which was a mixture of pulp and synthetic fiber, was used as the backing paper and the backing paper was not impregnated with ionizing radiation cross-linking material. Produced.
  • Test example 1 The adhesion between the resin layer and the backing paper was evaluated by peeling the resin layer of the foamed laminated sheet from the backing paper in the width direction.
  • the evaluation criteria are as follows. ⁇ : The resin layer brings the fiber of the backing paper over the entire width. ⁇ : The resin layer partially brings the backing paper fibers. X: The resin layer does not bring the fiber of the backing paper at all.
  • Test example 2 The underwater elongation of the foamed laminated sheet was evaluated. Specifically, the foamed laminated sheet is cut into dimensions of 5 cm in the MD direction and 11 cm in the TD direction, a 10 cm long marked line is drawn from the center of the MD direction to the width in the TD direction, and immersed in water for 1 hour. The rate of change was determined from the difference in the marked line length before and after immersion.
  • the evaluation criteria for elongation in water are as follows. ⁇ : Less than 0.6% ⁇ : 0.6% or more.
  • Test example 3 A predetermined amount of (1) methylcellulose adhesive (Methylan Special Henkel) and (2) starch adhesive (starch + synthetic resin) (made by Rua Mild Yayoi Chemical) are dissolved in water on the gypsum board surface. What was prepared as an adhesive agent was applied, and the backing paper surface of each foamed laminated sheet was laminated thereon and dried to obtain a test specimen. A 25 mm wide cut was made into the test piece and peeled off by hand, and the peeled surface was observed. The evaluation criteria are as follows. ⁇ : The backing paper is peeled off between the backing paper and the adhesive without remaining on the board surface. ⁇ : The backing paper is partially taken to the adhesive side. Heavy peeling. ⁇ * 1 : The backing paper peels off between the papers and remains on the base of the gypsum board. ⁇ * 2 : The gypsum board substrate peels off.
  • methylcellulose adhesive Metal Organic Chemical
  • starch + synthetic resin made by Rua Mild Yayoi Chemical

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The purpose of the present invention is to provide a novel laminate sheet and foam laminate sheet (generically referred to as "wallpaper or the like"), and, specifically, to provide a wallpaper or the like that can be easily applied after an adhesive is coated on an application surface, and that has a backing paper that can be detached from the adhesive during repapering, even when a combination of other than a synthetic fiber mixed paper and a methyl cellulose adhesive is used. Specifically, the present invention provides a laminate sheet in which at least a resin layer is laminated on a fibrous substrate, said laminate sheet characterized in that the fibrous substrate contains a crosslinking substance that comprises an ionizing radiation crosslinking material.

Description

積層シート及び発泡積層シート並びにそれらの製造方法及び施工方法LAMINATED SHEET, FOAM LAMINATED SHEET, ITS MANUFACTURING METHOD, AND CONSTRUCTION METHOD
　本発明は、積層シート及び発泡積層シート並びにそれらの製造方法及び施工方法に関する。 The present invention relates to a laminate sheet, a foam laminate sheet, and a production method and a construction method thereof.
　前記発泡積層シートは、発泡樹脂層を有しており、発泡壁紙、各種装飾材等として有用である。また、前記積層シートは、前記発泡積層シートの発泡前の状態（いわゆる未発泡原反）を意味するか又は発泡樹脂層を有していない状態で各種装飾材として有用なシートを意味する。 The foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like. The laminated sheet means a state before foaming of the foamed laminated sheet (so-called unfoamed raw fabric) or a sheet useful as various decorative materials in a state where no foamed resin layer is provided.
　従来、パルプ成分と合成樹脂成分とを混抄した裏打紙とメチルセルロース系接着剤とを組み合わせて壁紙などの装飾材の施工を行うことが知られており、例えば、特許文献1には、「少なくとも裏打ち紙と装飾層の積層構造からなる壁紙であって、この壁紙を壁面に接着剤を使用して施工した場合に、当該壁紙の前記壁面からの剥離が前記接着剤層で剥離され、前記接着剤がメチルセルロース系接着剤であって、前記壁紙の前記壁面からの剥離強度が100～500g/3cmであり、前記裏打ち紙が、パルプ成分と合成樹脂成分を混抄してなり、当該裏打ち紙の層間剥離強度が前記壁紙の前記壁面からの剥離強度より大きいことを特徴とする壁紙。」が開示されている。 Conventionally, it is known that a decorative material such as wallpaper is applied by combining a backing paper mixed with a pulp component and a synthetic resin component and a methylcellulose-based adhesive. A wallpaper having a laminated structure of paper and a decorative layer, and when the wallpaper is applied to a wall surface using an adhesive, peeling of the wallpaper from the wall surface is peeled off by the adhesive layer, and the adhesive Is a methylcellulose-based adhesive having a peeling strength of 100 to 500 g / 3 cm from the wall surface of the wallpaper, and the backing paper is a mixture of a pulp component and a synthetic resin component, and delamination of the backing paper Wallpapers characterized in that the strength is greater than the peel strength of the wallpaper from the wall surface. "
　上記パルプ成分と合成樹脂成分とを混抄した裏打紙は、合成繊維混抄紙特有の濡れ時の寸法変化の少なさ（水中伸度の少なさ）を利用して、被施工面である壁面に接着剤を塗工し、その後に当該裏打紙を有する壁紙を施工することを可能としている。被施工面への接着剤の塗工は一般消費者でも容易に行えるというメリットがある。また、メチルセルロース系接着剤と当該裏打紙とを組み合わせることにより、古くなった壁紙を貼り替える際に、裏打紙と接着剤との間で剥離することができ、被施工面への紙残りや被施工面を傷つけることが少なく、新たに貼着する壁紙に対しても影響が少ないというメリットがある。 The backing paper, which is a mixture of the above pulp component and synthetic resin component, is bonded to the wall surface, which is the construction surface, using the small dimensional change when wet (low elongation in water) unique to synthetic fiber mixed paper. It is possible to apply the agent and then to construct a wallpaper having the backing paper. There is an advantage that even an ordinary consumer can easily apply an adhesive to a work surface. In addition, by combining the methylcellulose adhesive and the backing paper, when replacing the old wallpaper, it can be peeled off between the backing paper and the adhesive, and the paper remaining on the construction surface or the coated paper can be removed. There is a merit that there is little damage to the construction surface and there is little influence on the newly stuck wallpaper.
　これに対して、他の裏打紙を用いる場合には、水中伸度が比較的大きいため、裏打紙に接着剤を塗工し、寸法が安定するまで時間をおいた後で被施工面に貼着する必要がある。また、貼着後も壁紙の寸法が変化する場合があるため、施工後の壁紙のジョイント部の目透き（隙間が開く）や突き上げが生じるおそれがある。更に、裏打紙に接着剤を塗工するには特別な接着剤塗工機が必要である上、接着剤を塗工後の壁紙の取り扱いも容易ではないため、専門業者による作業を余儀なくされている。 On the other hand, when using other backing paper, the elongation in water is relatively large, so apply adhesive to the backing paper and wait for a while until the dimensions stabilize, and then apply it to the work surface. It is necessary to wear. In addition, since the size of the wallpaper may change even after sticking, there is a possibility that the joint portion of the wallpaper after construction (clearance opens) or push-up may occur. In addition, a special adhesive coating machine is required to apply the adhesive to the backing paper, and it is not easy to handle the wallpaper after the adhesive is applied. Yes.
　また、壁紙施工に用いる接着剤としては、メチルセルロース系接着剤以外にデンプン系接着剤（デンプン糊、デンプン糊に合成樹脂を添加したもの）が一般に用いられるが、デンプン系接着剤の場合には、裏打紙と接着剤との接着強度が強すぎて、古くなった壁紙を貼り替える際に、紙間剥離が生じて被施工面に裏打紙が残ったり被施工面を傷つけたりする場合がある。 In addition, as an adhesive used for wallpaper construction, a starch adhesive (starch paste, starch paste with a synthetic resin added) is generally used in addition to a methylcellulose adhesive. In the case of a starch adhesive, The adhesive strength between the backing paper and the adhesive is too strong, and when replacing an old wallpaper, separation between papers may occur, and the backing paper may remain on the construction surface or damage the construction surface.
　よって、合成繊維混抄紙とメチルセルロース系接着剤との組み合わせ以外においても、被施工面に接着剤を塗工した後に容易に壁紙などの施工ができ、しかも古くなった壁紙などを貼り替える際に裏打紙と接着剤との間で剥離することが望まれている。 Therefore, other than the combination of synthetic fiber mixed paper and methylcellulose adhesive, wallpaper can be easily applied after the adhesive is applied to the work surface, and the backing is used when replacing old wallpaper. It is desired to peel between the paper and the adhesive.
特許第4205562号公報Japanese Patent No. 4205562
　本発明は、新規な積層シート及び発泡積層シート（「壁紙など」と総称する）を提供することを目的とし、詳細には、合成繊維混抄紙とメチルセルロース系接着剤との組み合わせ以外においても、被施工面に接着剤を塗工した後に容易に施工することができ、しかも貼り替える際に裏打紙と接着剤との間で剥離することが可能な壁紙などを提供することを目的とする。 An object of the present invention is to provide a novel laminated sheet and a foamed laminated sheet (collectively referred to as “wallpaper or the like”), and more specifically, in addition to a combination of a synthetic fiber mixed paper and a methylcellulose-based adhesive. An object of the present invention is to provide a wallpaper or the like that can be easily applied after the adhesive is applied to the construction surface and that can be peeled off between the backing paper and the adhesive when the adhesive is replaced.
　本発明者は、鋭意研究を重ねた結果、壁紙などの裏打紙として電離放射線架橋型材料の架橋物を含有する繊維質基材を用いる場合には、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the above object can be achieved when a fibrous base material containing a cross-linked product of ionizing radiation cross-linking material is used as a backing paper such as wallpaper. It came to be completed.
　即ち、本発明は、下記の積層シート、発泡積層シート及びそれらの製造方法に関する。
1. 繊維質基材上に少なくとも樹脂層が積層されている積層シートであって、前記繊維質基材は電離放射線架橋型材料の架橋物を含有することを特徴とする積層シート。
2. 前記樹脂層がオレフィン系樹脂層である、上記項1に記載の積層シート。
3. 前記樹脂層が発泡剤含有樹脂層である、又は発泡剤含有樹脂層を含む積層体からなる層である、上記項1又は2に記載の積層シート。
4. 前記発泡剤含有樹脂層は、片面又は両面に非発泡樹脂層を有する、上記項3に記載の積層シート。
5. 前記発泡剤含有樹脂層は、電子線照射により樹脂架橋されている、上記項3又は4に記載の積層シート。
6. 上記項3～5のいずれかに記載の積層シートの発泡剤含有樹脂層を発泡させることにより得られる発泡積層シート。
7. （1）繊維質基材上に少なくとも樹脂層を形成する工程と、
（2）前記繊維質基材に電離放射線架橋型材料を含浸する工程と、を有し、
上記2つの工程を経た後に、少なくとも前記繊維質基材に電離放射線を照射し、前記電離放射線架橋型材料を架橋させることにより架橋物を形成することを特徴とする積層シートの製造方法。
8. 前記繊維質基材上に少なくとも前記樹脂層を押出し製膜により形成する、上記項7に記載の積層シートの製造方法。
9. 前記樹脂層が発泡剤含有樹脂層である、又は発泡剤含有樹脂層を含む積層体からなる層であり、且つ、前記電離放射線が電子線であり、前記電子線の照射により、前記電離放射線架橋型材料の架橋と前記発泡剤含有樹脂層の樹脂架橋とを同時に行う、上記項7又は8に記載の積層シートの製造方法。
10. 前記樹脂層が発泡剤含有樹脂層である、又は発泡剤含有樹脂層を含む積層体からなる層である、上記項7～9のいずれかに記載の製造方法により製造される積層シートの前記発泡剤含有樹脂層を加熱により発泡させる発泡積層シートの製造方法。
11. 接着剤を塗工した被施工面に上記項1～6のいずれかに記載の積層シート又は発泡積層シートを貼着することを特徴とする施工方法。
12. 上記項1～6のいずれかに記載の積層シート又は発泡積層シートの裏側に接着剤を塗工後、被施工面に貼着することを特徴とする施工方法。
13. 前記被施工面は、壁面及び／又は天井である、上記項11又は12に記載の施工方法。 That is, the present invention relates to the following laminated sheets, foamed laminated sheets, and methods for producing them.
1. A laminated sheet in which at least a resin layer is laminated on a fibrous base material, wherein the fibrous base material contains a cross-linked product of an ionizing radiation cross-linkable material.
2. The laminated sheet according to item 1, wherein the resin layer is an olefin resin layer.
3. The laminated sheet according to item 1 or 2, wherein the resin layer is a foaming agent-containing resin layer or a layer composed of a laminate including the foaming agent-containing resin layer.
4. The laminated sheet according to item 3, wherein the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides.
5. The laminated sheet according to Item 3 or 4, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.
6. A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of items 3 to 5.
7. (1) forming at least a resin layer on the fibrous base material;
(2) impregnating the fibrous base material with an ionizing radiation cross-linking material,
A method for producing a laminated sheet, wherein a cross-linked product is formed by irradiating at least the fibrous base material with ionizing radiation and cross-linking the ionizing radiation cross-linking material after passing through the two steps.
8. The method for producing a laminated sheet according to item 7, wherein at least the resin layer is formed on the fibrous base material by extrusion film formation.
9. The resin layer is a foaming agent-containing resin layer, or a layer composed of a laminate including a foaming agent-containing resin layer, and the ionizing radiation is an electron beam. Item 9. The method for producing a laminated sheet according to Item 7 or 8, wherein the crosslinking of the radiation crosslinking material and the resin crosslinking of the foaming agent-containing resin layer are simultaneously performed.
10. The laminated sheet produced by the production method according to any one of the above items 7 to 9, wherein the resin layer is a foaming agent-containing resin layer, or a layer comprising a laminate including the foaming agent-containing resin layer. The manufacturing method of the foaming lamination sheet which foams the said foaming agent containing resin layer by heating.
11. A construction method comprising sticking the laminated sheet or foam laminated sheet according to any one of the above items 1 to 6 to a work surface coated with an adhesive.
12. A construction method characterized in that an adhesive is applied to the back side of the laminated sheet or foamed laminated sheet according to any one of items 1 to 6 and then adhered to the construction surface.
13. The construction method according to Item 11 or 12, wherein the construction surface is a wall surface and / or a ceiling.
　本発明の積層シートは、繊維質基材が電離放射線架橋型材料の架橋物を含有することにより、繊維質基材の繊維材料の種類に関わらず、前記架橋物を含有することで水中伸度（寸法変化）が少なく抑えられている。そのため、被施工面に接着剤を塗工した後に容易に施工することができ、しかも接着剤の種類に関わらず、貼り替える際に繊維質基材と接着剤との間で剥離することができる。この効果は、本発明の積層シート及び発泡積層シートのいずれでも得られる。このような本発明の積層シート及び発泡積層シートは、一般消費者が容易に施工（貼着）及び貼り替えができる点で優位性が大きい。 In the laminated sheet of the present invention, the fibrous base material contains a cross-linked product of an ionizing radiation cross-linkable material. (Dimensional change) is suppressed to a minimum. Therefore, it can be easily applied after the adhesive is applied to the work surface, and can be peeled off between the fibrous base material and the adhesive when reattaching regardless of the type of adhesive. . This effect can be obtained by both the laminated sheet and the foamed laminated sheet of the present invention. Such a laminated sheet and foamed laminated sheet of the present invention have a great advantage in that general consumers can easily construct (stick) and replace them.
本発明の積層シートの層構成の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the lamination sheet of this invention.
　以下、本発明の積層シート及び発泡積層シート並びにそれらの製造方法及び施工方法について詳細に説明する。 Hereinafter, the laminated sheet and the foamed laminated sheet of the present invention, and the production method and construction method thereof will be described in detail.
　≪積層シート≫
　本発明の積層シートは、繊維質基材上に少なくとも樹脂層が積層されている積層シートであって、前記繊維質基材は電離放射線架橋型材料の架橋物を含有することを特徴とする。 ≪Laminated sheet≫
The laminated sheet of the present invention is a laminated sheet in which at least a resin layer is laminated on a fibrous base material, and the fibrous base material contains a cross-linked product of an ionizing radiation cross-linkable material.
　上記特徴を有する本発明の積層シートは、繊維質基材が電離放射線架橋型材料の架橋物を含有することにより、繊維質基材の繊維材料の種類に関わらず、前記架橋物を含有することで水中伸度（寸法変化）が少なく抑えられている。そのため、被施工面に接着剤を塗工した後に容易に施工することができ、しかも接着剤の種類に関わらず、貼り替える際に繊維質基材と接着剤との間で剥離することができる。この効果は、本発明の積層シート及び発泡積層シートのいずれでも得られる。このような本発明の積層シート及び発泡積層シートは、一般消費者が容易に施工（貼着）及び貼り替えができる点で優位性が大きい。 The laminated sheet of the present invention having the above characteristics contains the cross-linked product regardless of the type of the fiber material of the fibrous base material because the fibrous base material contains a cross-linked product of the ionizing radiation cross-linking material. The underwater elongation (dimensional change) is suppressed to a minimum. Therefore, it can be easily applied after the adhesive is applied to the work surface, and can be peeled off between the fibrous base material and the adhesive when reattaching regardless of the type of adhesive. . This effect can be obtained by both the laminated sheet and the foamed laminated sheet of the present invention. Such a laminated sheet and foamed laminated sheet of the present invention have a great advantage in that general consumers can easily construct (stick) and replace them.
　以下、積層シートを構成する各層について説明する。なお、本明細書では、繊維質基材から見て樹脂層が積層されている方向を「上」又は「おもて面」と称し、繊維質基材から見て樹脂層が積層されている方向とは逆側を「下」又は「裏面」と称する。 Hereinafter, each layer constituting the laminated sheet will be described. In this specification, the direction in which the resin layer is laminated as viewed from the fibrous base material is referred to as “upper” or “front surface”, and the resin layer is laminated from the fibrous base material. The side opposite to the direction is referred to as “down” or “back surface”.
　繊維質基材
　繊維質基材としては、電離放射線架橋型材料の架橋物を含有するものを用いる。ここで、電離放射線架橋型材料の架橋物は、繊維質基材（繊維質シートの状態にあるもの）に電離放射線架橋型材料を含浸（含浸には浸漬、塗布、噴霧等の各種の態様が含まれる）させた後に電離放射線を照射することにより形成する。 Fibrous base material As the fibrous base material, one containing a cross-linked product of ionizing radiation cross-linking material is used. Here, the cross-linked product of the ionizing radiation cross-linking material is impregnated with the ionizing radiation cross-linking material in a fibrous base material (one in a fibrous sheet) (impregnation includes various modes such as dipping, coating, spraying, etc.). It is formed by irradiating with ionizing radiation.
　繊維質シートとしては、具体的には、壁紙用一般紙（パルプ主体のシートを既知のサイズ剤でサイズ処理したもの）；難燃紙（パルプ主体のシートをスルファミン酸グアニジン、リン酸グアジニン等の難燃剤で処理したもの）；水酸化アルミニウム、水酸化マグネシウム等の無機添加剤を含む無機質紙；上質紙；薄用紙；合成繊維混抄紙（パルプと合成繊維とを混合して抄紙したもの）などが挙げられる。 Specific examples of the fibrous sheet include wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet such as guanidine sulfamate, guanidine phosphate, etc. Treated with flame retardant); inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; synthetic fiber mixed paper (paper made by mixing pulp and synthetic fiber), etc. Is mentioned.
　なお、本発明に使用される繊維質シートには、分類上、不織布に該当しているものも包含される。本発明においては、樹脂層との密着性を良好とする観点から、上記で例示した繊維質シートのうち、壁紙用一般紙、難燃紙を用いることが好ましい。 The fibrous sheet used in the present invention includes those that fall under the category of nonwoven fabric. In the present invention, from the viewpoint of improving the adhesion to the resin layer, it is preferable to use general paper for wallpaper and flame retardant paper among the fibrous sheets exemplified above.
　繊維質シートの坪量は限定的ではないが、50～300g/m2程度が好ましく、50～130g/m2程度がより好ましい。 Although the basis weight of the fibrous sheet is not critical, preferably about 50 ~ 300g / m 2, more preferably about 50 ~ 130g / m 2.
　電離放射線架橋型材料としては特に限定されず、紫外線、電子線等の電離放射線の照射により架橋反応（重合架橋反応）可能なラジカル重合性不飽和基やカチオン重合性官能基を分子中に含むプレポリマー（オリゴマーを含む）及び／又はモノマーを主成分とする化合物が使用できる。これらのプレポリマー又はモノマーは、単体又は複数を混合して使用でき、繊維質基材への浸透性を考慮すると比較的粘度が低いモノマーが好ましい。 The ionizing radiation crosslinkable material is not particularly limited, and a prepolymer containing in the molecule a radical polymerizable unsaturated group or a cationic polymerizable functional group capable of performing a crosslinking reaction (polymerization crosslinking reaction) by irradiation with ionizing radiation such as ultraviolet rays and electron beams. Polymers (including oligomers) and / or compounds based on monomers can be used. These prepolymers or monomers can be used alone or in combination, and monomers having a relatively low viscosity are preferred in consideration of permeability to the fibrous base material.
　具体的には、前記プレポリマー又はモノマーとしては、分子中に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基等のラジカル重合性不飽和基、エポキシ基等のカチオン重合性官能基等を有する化合物が挙げられる。また、ポリエンとポリチオールとの組み合わせによるポリエン／チオール系のプレポリマーも好ましい。ここで、（メタ）アクリロイル基とは、アクリロイル基又はメタクリロイル基の意味である。 Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.
　ラジカル重合性不飽和基を有するプレポリマーとしては、例えば、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、メラミン（メタ）アクリレート、トリアジン（メタ）アクリレート、シリコーン（メタ）アクリレート等が挙げられる。これらの分子量は、通常250～100000程度が好ましい。 Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.
　ラジカル重合性不飽和基を有するモノマーとしては、例えば、単官能モノマーとして、メチル（メタ）アクリレート、2－エチルヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。また、多官能モノマーとしては、例えば、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジメタクリレート、トリメチールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイドトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 Examples of the monomer having a radical polymerizable unsaturated group include, as monofunctional monomers, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide tri (meth) acrylate. , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
　カチオン重合性官能基を有するプレポリマーとしては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ化合物等のエポキシ系樹脂、脂肪酸系ビニルエーテル、芳香族系ビニルエーテル等のビニルエーテル系樹脂のプレポリマーが挙げられる。また、チオールとしては、例えば、トリメチロールプロパントリチオグリコレート、ペンタエリスリトールテトラチオグリコレート等のポリチオールが挙げられる。ポリエンとしては、例えば、ジオール及びジイソシアネートによるポリウレタンの両端にアリルアルコールを付加したものが挙げられる。 Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.
　電離放射線架橋型材料としては、架橋反応を促進するため、これらのプレポリマー又はモノマーとして、１分子中に２つ以上の重合性官能基を有する多官能プレポリマー又は多官能モノマーを用いることが好ましい。 As the ionizing radiation crosslinking material, it is preferable to use a polyfunctional prepolymer or a polyfunctional monomer having two or more polymerizable functional groups in one molecule as these prepolymers or monomers in order to promote a crosslinking reaction. .
　電離放射線架橋型材料としては、これらのプレポリマー又はモノマーをその他の材料と組み合わせた材料を使用してもよい。これらのプレポリマー又はモノマーと組み合わせて使用される材料としては、例えば、一般的な塗料として慣用されているアクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂等の樹脂が挙げられる。これらのプレポリマー又はモノマーをこれらの樹脂と組み合わせて使用する場合、プレポリマー又はモノマーは、これらの樹脂を架橋する架橋剤として機能するものであってもよい。 As the ionizing radiation crosslinking material, a material obtained by combining these prepolymers or monomers with other materials may be used. Examples of materials used in combination with these prepolymers or monomers include resins such as acrylic resins, urethane resins, epoxy resins, and polyester resins that are commonly used as general paints. When these prepolymers or monomers are used in combination with these resins, the prepolymers or monomers may function as a crosslinking agent that crosslinks these resins.
　電離放射線架橋型材料を架橋させるために用いる電離放射線としては、電離放射線架橋型材料中の分子を架橋反応させ得るエネルギーを有する電磁波又は荷電粒子が用いられる。通常は紫外線又は電子線を用いればよいが、可視光線、Ｘ線、イオン線等を用いてもよい。 As the ionizing radiation used for cross-linking the ionizing radiation cross-linking material, electromagnetic waves or charged particles having energy capable of cross-linking the molecules in the ionizing radiation cross-linking material are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.
　紫外線源としては、例えば、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク灯、ブラックライト、メタルハライドランプ等の光源が使用できる。紫外線の波長としては、通常190～380nmが好ましい。 As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. The wavelength of ultraviolet light is usually preferably 190 to 380 nm.
　電子線源としては、例えば、コッククロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、又は直線型、ダイナミトロン型、高周波型等の各種電子線加速器が使用できる。その中でも、特に100～1000keV、好ましくは100～300keVのエネルギーをもつ電子を照射できるものが好ましい。 As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.
　電離放射線架橋型材料の架橋物を含有する繊維質基材の密度は架橋物を含有する前の繊維質基材の種類や架橋物の含有量により異なるが、坪量が65g/m2程度の繊維質シートを用いた場合には、架橋物を含有する繊維質基材の密度は0.60～0.65g/cm3程度であり、水酸化アルミニウム等の無機添加剤を含む無機質紙を用いた場合には、1.0g/cm3程度である。また、架橋物を含有する繊維質基材の紙間強度は、坪量が65g/m2程度の繊維質シートを用いた場合には、0.25～3.8N/（3cm巾）程度である。 Although the density of the fibrous base material containing a crosslinked product of an ionizing radiation crosslinked materials differs by content type and cross-linking of the fibrous base material before containing crosslinked product, basis weight of 65 g / m 2 of about When the fiber sheet is used, the density of the fiber base material containing the cross-linked product is about 0.60 to 0.65 g / cm 3 , and when the inorganic paper containing an inorganic additive such as aluminum hydroxide is used. Is about 1.0 g / cm 3 . Further, the inter-paper strength of the fibrous base material containing the crosslinked product is about 0.25 to 3.8 N / (3 cm width) when a fibrous sheet having a basis weight of about 65 g / m 2 is used.
　樹脂層
　本発明の積層シートは、繊維質基材の上に少なくとも樹脂層が積層されている。この樹脂層は、Tダイ製膜法、カレンダー製膜法等の既知の製膜法により形成できる。 Resin layer In the laminated sheet of the present invention, at least a resin layer is laminated on a fibrous base material. This resin layer can be formed by a known film forming method such as a T-die film forming method or a calendar film forming method.
　樹脂層に含まれる樹脂成分としては、従来から壁装材に用いられている塩化ビニル樹脂、オレフィン系樹脂等が広く採用できるが、塩化ビニル樹脂は可塑剤が経時的にブリードするおそれがあることから、積層シートの耐久性を高める観点では塩化ビニル樹脂よりもオレフィン系樹脂が好ましく、具体的には、エチレン系樹脂を含有することが好ましい。 As the resin component contained in the resin layer, vinyl chloride resins and olefin resins conventionally used for wall covering materials can be widely used. However, the vinyl chloride resin may cause the plasticizer to bleed over time. Therefore, from the viewpoint of enhancing the durability of the laminated sheet, an olefin resin is preferable to a vinyl chloride resin, and specifically, an ethylene resin is preferably contained.
　エチレン系樹脂としては、ポリエチレン（PE）だけでなく、エチレンとエチレン以外の成分とをモノマーとするエチレン共重合体（以下、「エチレン共重合体」と略記する）が挙げられる。 Examples of the ethylene-based resin include not only polyethylene (PE) but also ethylene copolymers having monomers other than ethylene and ethylene (hereinafter, abbreviated as “ethylene copolymers”).
　ポリエチレンは、低密度ポリエチレン（LDPE）、中密度ポリエチレン（MDPE）、高密度ポリエチレン（HDPE）、直鎖状低密度ポリエチレン（LLDPE）等が広く使用できる。 As the polyethylene, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and the like can be widely used.
　エチレン共重合体は融点及びMFRの観点で押出し製膜に適している。エチレン共重合体としては、例えば、エチレン－酢酸ビニル共重合体（EVA）、エチレン－メチルメタクリレート共重合体（EMMA）、エチレン－アクリル酸共重合体（EAA）、エチレン－エチルアクリレート共重合体（EEA）、エチレン－メチルアクリレート共重合体（EMA）、エチレン－メタクリル酸共重合体（EMAA）、エチレン－αオレフィン共重合体等が挙げられる。これらのエチレン共重合体は単独又は2種以上を混合して使用できる。これらのエチレン共重合体の中でも特にエチレン－酢酸ビニル共重合体、エチレン－メチルメタクリレート共重合体が好ましく、これらのいずれか1種と他の樹脂の1種以上とを併用する場合には、エチレン－酢酸ビニル共重合体、エチレン－メチルメタクリレート共重合体の含有量は、それぞれ70重量％以上が好ましく、80重量％以上がより好ましい。 Ethylene copolymer is suitable for extrusion film formation from the viewpoint of melting point and MFR. Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-acrylic acid copolymer (EAA), and an ethylene-ethyl acrylate copolymer ( EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-α olefin copolymer, and the like. These ethylene copolymers can be used alone or in admixture of two or more. Among these ethylene copolymers, ethylene-vinyl acetate copolymer and ethylene-methyl methacrylate copolymer are particularly preferred. When any one of these is used in combination with one or more other resins, ethylene -The content of vinyl acetate copolymer and ethylene-methyl methacrylate copolymer is preferably 70% by weight or more, and more preferably 80% by weight or more.
　また、エチレン共重合体は、エチレン以外のモノマーの含有量としては、5～25重量％が好ましく、9～20重量％がより好ましい。このような共重合比率を採用することにより、押出し製膜性がより高まる。具体例としては、エチレン－酢酸ビニル共重合体は、酢酸ビニルの共重合比率（VA量）としては9～25重量％が好ましく、9～20重量％がより好ましい。また、エチレン－メチルメタクリレート共重合体は、メチルメタクリレートの共重合比率（MMA量）としては5～25重量％が好ましく、5～15重量％がより好ましい。また、エチレン－メタクリル酸共重合体は、アクリル酸の共重合比率（MAA量）としては2～15質量％が好ましく、5～11質量％がより好ましい。 In the ethylene copolymer, the content of monomers other than ethylene is preferably 5 to 25% by weight, more preferably 9 to 20% by weight. By adopting such a copolymerization ratio, the extrusion film forming property is further enhanced. As a specific example, the ethylene-vinyl acetate copolymer has a vinyl acetate copolymerization ratio (VA amount) of preferably 9 to 25% by weight, more preferably 9 to 20% by weight. The ethylene-methyl methacrylate copolymer has a methyl methacrylate copolymerization ratio (MMA amount) of preferably 5 to 25% by weight, more preferably 5 to 15% by weight. The ethylene-methacrylic acid copolymer preferably has a copolymerization ratio (MAA amount) of acrylic acid of 2 to 15% by mass, more preferably 5 to 11% by mass.
　また、本発明では、樹脂層に含まれる樹脂成分は、製膜方法にもよるが、JIS K 6922に記載の190℃、荷重21.18Nの条件で測定したMFR（メルトフローレート）が10～40g/10分であることが好ましい。MFRが上記範囲内の場合には、樹脂層を押出し製膜により形成する際の温度上昇が少なく、非発泡状態で製膜できるため、後に絵柄模様層を形成する場合には、平滑な面に印刷処理をすることができて柄抜け等が少ない。MFRが大きすぎる場合は、樹脂が軟らかすぎることにより、形成される樹脂層の耐傷性が不十分となるおそれがある。 In the present invention, the resin component contained in the resin layer has an MFR (melt flow rate) of 10 to 40 g measured at 190 ° C. and a load of 21.18 N described in JIS K-6922, depending on the film forming method. / 10 minutes is preferred. When the MFR is within the above range, the temperature rise when forming the resin layer by extrusion film formation is small, and the film can be formed in a non-foamed state. The printing process can be performed, and there are few missing patterns. If the MFR is too large, the resin is too soft and the resulting resin layer may have insufficient scratch resistance.
　本発明では、上記樹脂層は発泡剤含有樹脂層であってもよく、発泡剤含有樹脂層を含む積層体からなる層であってもよい。これらの場合には、得られる積層シートは発泡剤含有樹脂層を有するいわゆる原反を意味する。そして、発泡剤含有樹脂層を発泡させることにより、本発明の発泡積層シートが得られる。 In the present invention, the resin layer may be a foaming agent-containing resin layer or a layer formed of a laminate including the foaming agent-containing resin layer. In these cases, the obtained laminated sheet means a so-called original fabric having a foaming agent-containing resin layer. And the foaming lamination sheet of this invention is obtained by making a foaming agent containing resin layer foam.
　発泡剤含有樹脂層を形成する樹脂組成物としては、例えば、上記樹脂成分、無機充填剤、顔料、熱分解型発泡剤、発泡助剤、架橋助剤等を含む樹脂組成物を好適に使用できる。その他にも、安定剤、滑剤等を添加剤として使用できる。 As the resin composition for forming the foaming agent-containing resin layer, for example, a resin composition containing the above resin component, inorganic filler, pigment, pyrolytic foaming agent, foaming aid, crosslinking aid and the like can be suitably used. . In addition, stabilizers, lubricants and the like can be used as additives.
　熱分解型発泡剤としては、例えば、アゾジカルボンアミド（ADCA）、アゾビスホルムアミド等のアゾ系；オキシベンゼンスルホニルヒドラジド（OBSH）、パラトルエンスルホニルヒドラジド等のヒドラジド系などが挙げられる。熱分解型発泡剤の含有量は、発泡剤の種類、発泡倍率等に応じて適宜設定できる。発泡倍率の観点からは、7倍以上、好ましくは7～10倍程度であり、熱分解型発泡剤は、樹脂成分100質量部に対して、1～20質量部程度とすることが好ましい。 Examples of the thermally decomposable foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 7 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.
　発泡助剤は、金属酸化物及び／又は脂肪酸金属塩が好ましく、例えば、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、オクチル酸亜鉛、オクチル酸カルシウム、オクチル酸マグネシウム、ラウリン酸亜鉛、ラウリン酸カルシウム、ラウリン酸マグネシウム、酸化亜鉛、酸化マグネシウム等を使用することができる。これらの発泡助剤の含有量は、樹脂成分100質量部に対して、0.3～10質量部程度が好ましく、1～5質量部程度がより好ましい。 The foaming aid is preferably a metal oxide and / or a fatty acid metal salt. For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, laurin Magnesium acid, zinc oxide, magnesium oxide and the like can be used. The content of these foaming auxiliaries is preferably about 0.3 to 10 parts by mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the resin component.
　なお、これらの発泡助剤とEMAAとADCA発泡剤とを組み合わせて用いる場合には、発泡工程において、EMAAのアクリル酸部と金属系発泡助剤の反応により、発泡助剤としての効果が損なわれるという問題がある。そのため、EMAAとADCA発泡剤とを組み合わせて用いる場合には、特開2009-197219号公報に説明されている通り、発泡助剤としてカルボン酸ヒドラジド化合物を用いることが好ましい。このとき、カルボン酸ヒドラジド化合物はADCA発泡剤1質量部に対して0.2～1質量部程度用いることが好ましい。 When these foaming aids are used in combination with EMAA and ADCA foaming agents, the effect of the foaming aid is impaired by the reaction between the acrylic acid part of EMAA and the metallic foaming aid in the foaming process. There is a problem. Therefore, when EMAA and ADCA foaming agent are used in combination, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid as described in JP-A-2009-197219. At this time, the carboxylic acid hydrazide compound is preferably used in an amount of about 0.2 to 1 part by mass with respect to 1 part by mass of the ADCA foaming agent.
　無機充填剤としては、例えば、炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、三酸化アンチモン、ホウ酸亜鉛、モリブデン化合物等が挙げられる。無機充填剤を含むことにより、目透き抑制効果、表面特性向上効果、燃焼時発熱抑制効果等が得られる。無機充填剤の含有量は、樹脂成分100質量部に対して0～100質量部程度が好ましく、20～70質量部程度がより好ましい。 Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including the inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, an effect of suppressing heat generation during combustion, and the like are obtained. The content of the inorganic filler is preferably about 0 to 100 parts by mass and more preferably about 20 to 70 parts by mass with respect to 100 parts by mass of the resin component.
　顔料については、無機顔料として、例えば、酸化チタン、亜鉛華、カーボンブラック、黒色酸化鉄、黄色酸化鉄、黄鉛、モリブデートオレンジ、カドミウムイエロー、ニッケルチタンイエロー、クロムチタンイエロー、酸化鉄（弁柄）、カドミウムレッド、群青、紺青、コバルトブルー、酸化クロム、コバルトグリーン、アルミニウム粉、ブロンズ粉、雲母チタン、硫化亜鉛等が挙げられる。また、有機顔料として、例えば、アニリンブラック、ペリレンブラック、アゾ系（アゾレーキ、不溶性アゾ、縮合アゾ）、多環式（イソインドリノン、イソインドリン、キノフタロン、ペリノン、フラバントロン、アントラピリミジン、アントラキノン、キナクリドン、ペリレン、ジケトピロロピロール、ジブロムアンザントロン、ジオキサジン、チオインジゴ、フタロシアニン、インダントロン、ハロゲン化フタロシアニン）等が挙げられる。顔料の含有量は、樹脂成分100質量部に対して10～50質量部程度が好ましく、15～30質量部程度がより好ましい。 For pigments, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve) ), Cadmium red, ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone. Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine). The content of the pigment is preferably about 10 to 50 parts by mass, more preferably about 15 to 30 parts by mass with respect to 100 parts by mass of the resin component.
　本発明では、発泡剤含有樹脂層は電子線照射により樹脂架橋されていてもよい。発泡剤含有樹脂層に電子線を照射する方法及び発泡させる方法としては、後記の製造方法に記載された方法に従って実施すればよい。なお、本発明では、特に繊維質基材に照射する電離放射線が電子線である場合には、電離放射線架橋型材料の架橋と発泡剤含有樹脂層の樹脂架橋とを同時に行うこともできる。 In the present invention, the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. What is necessary is just to implement according to the method described in the postscript manufacturing method as a method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam. In the present invention, particularly when the ionizing radiation applied to the fibrous base material is an electron beam, crosslinking of the ionizing radiation-crosslinking material and resin crosslinking of the foaming agent-containing resin layer can be performed simultaneously.
　また、本発明において、樹脂層は、後述する絵柄模様層とは別に絵柄を形成する樹脂層であってもよい。使用する顔料や樹脂は後述の絵柄模様層に使用できるもの同じである。また、樹脂層は、電離放射線硬化性樹脂、熱硬化性樹脂（常温硬化性樹脂、２液反応硬化性樹脂を含む）等からなる樹脂層であってもよい。 In the present invention, the resin layer may be a resin layer that forms a pattern separately from the pattern layer described later. The pigments and resins used are the same as those that can be used in the pattern layer described later. The resin layer may be a resin layer made of an ionizing radiation curable resin, a thermosetting resin (including a room temperature curable resin, a two-component reaction curable resin), or the like.
　なお、樹脂層（単層又は多層の場合の両方を含む）の厚さは40～200μm程度が好ましく、樹脂層が発泡剤含有樹脂層であるか、又は発泡剤含有樹脂層を含む積層体からなる層である場合の、発泡後の樹脂層（単層又は多層の場合の両方を含む）の厚さは300～1000μm程度が好ましい。 The thickness of the resin layer (including both single layer and multilayer) is preferably about 40 to 200 μm, and the resin layer is a foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer. In the case of the layer to be formed, the thickness of the resin layer after foaming (including both single layer and multilayer) is preferably about 300 to 1000 μm.
　非発泡樹脂層A及びB
　発泡剤含有樹脂層は、その片面又は両面に非発泡樹脂層を有していてもよい。 Non-foamed resin layers A and B
The foaming agent-containing resin layer may have a non-foamed resin layer on one side or both sides.
　例えば、発泡剤含有樹脂層の裏面（繊維質基材が積層される面）には、繊維質基材との接着力を向上させる目的で非発泡樹脂層B（接着樹脂層）を有してもよい。 For example, the back surface (surface on which the fibrous base material is laminated) of the foaming agent-containing resin layer has a non-foamed resin layer B (adhesive resin layer) for the purpose of improving the adhesive strength with the fibrous base material. Also good.
　接着樹脂層の樹脂成分としては、特に限定はないが、エチレン－酢酸ビニル共重合体（EVA）が好ましい。EVAは公知又は市販のものを使用することができる。特に、酢酸ビニル成分（VA成分）が10～46質量％であるものが好ましく、15～41質量％であるものがより好ましい。 The resin component of the adhesive resin layer is not particularly limited, but ethylene-vinyl acetate copolymer (EVA) is preferable. As the EVA, a known or commercially available EVA can be used. In particular, the vinyl acetate component (VA component) is preferably 10 to 46% by mass, more preferably 15 to 41% by mass.
　接着樹脂層の厚さは限定的ではないが、3～50μｍ程度が好ましく、5～20μm程度がより好ましい。 The thickness of the adhesive resin layer is not limited, but is preferably about 3 to 50 μm, more preferably about 5 to 20 μm.
　発泡剤含有樹脂層の上面には、絵柄模様層を形成する際の絵柄模様を鮮明にしたり発泡樹脂層の耐傷性を向上させたりする目的で非発泡樹脂層Aを形成してもよい。 The non-foamed resin layer A may be formed on the upper surface of the foaming agent-containing resin layer for the purpose of clarifying the pattern when the pattern layer is formed or improving the scratch resistance of the foamed resin layer.
　非発泡樹脂層Aの樹脂成分としては、ポリオレフィン系樹脂、メタクリル系樹脂、熱可塑性ポリエステル系樹脂、ポリビニルアルコール系樹脂、フッ素系樹脂等が挙げられ、その中でもポリオレフィン系樹脂が好ましい。 Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluorine resins, and the like, among which polyolefin resins are preferable.
　ポリオレフィン系樹脂としては、例えば、ポリエチレン（低密度ポリエチレン（LDPE）又は高密度ポリエチレン（HDPE））、ポリプロピレン、ポリブテン、ポリブタジエン、ポリイソプレン等の樹脂単体、エチレンと炭素数が4以上のαオレフィンの共重合体（線状低密度ポリエチレン（LLDPE））、エチレン－アクリル酸共重合体、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸エチル共重合体、エチレン－メタクリル酸共重合体等のエチレン（メタ）アクリル酸系共重合体、エチレン－酢酸ビニル共重合体（EVA）、エチレン－酢酸ビニル共重合体ケン化物、エチレン－ビニルアルコール共重合体、アイオノマー等の少なくとも1種が挙げられる。本発明では、特に発泡剤含有樹脂層中の樹脂として塩化ビニル樹脂を用いる場合には、積層シートの耐久性を得るために、非発泡樹脂層A（特にエチレン－ビニルアルコール共重合体層）を形成することが好ましい。なお、「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味し、他の（メタ）と記載された部分についても同様である。 Examples of polyolefin resins include polyethylene (low density polyethylene (LDPE) or high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, and ethylene and α-olefins having 4 or more carbon atoms. Polymers (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer and other ethylene ( Examples thereof include at least one of a (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer (EVA), an ethylene-vinyl acetate copolymer saponified product, an ethylene-vinyl alcohol copolymer, and an ionomer. In the present invention, in particular, when a vinyl chloride resin is used as the resin in the foaming agent-containing resin layer, in order to obtain durability of the laminated sheet, the non-foamed resin layer A (particularly an ethylene-vinyl alcohol copolymer layer) is used. Preferably formed. In addition, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the same applies to other parts described as (meth).
　非発泡樹脂層Aの厚さは限定的ではないが、2～50μm程度が好ましく、5～20μｍ程度がより好ましい。 The thickness of the non-foamed resin layer A is not limited, but is preferably about 2 to 50 μm, more preferably about 5 to 20 μm.
　本発明では、後記製造上の観点からも、非発泡樹脂層B、発泡剤含有樹脂層及び非泡樹脂層Aが順に形成された態様が好ましい。 In the present invention, an embodiment in which the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are formed in order from the viewpoint of manufacturing described later is also preferable.
　絵柄模様層
　本発明の積層シートは、樹脂層（発泡剤含有樹脂層、非発泡樹脂層A等）又は後述のプライマー層の上には、必要に応じて絵柄模様層を形成してもよい。 Pattern Pattern Layer In the laminated sheet of the present invention, a pattern pattern layer may be formed on a resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.) or a primer layer described later, if necessary.
　絵柄模様層は、積層シート及び発泡積層シートに意匠性を付与する。絵柄模様としては、例えば木目模様、石目模様、砂目模様、タイル貼模様、煉瓦積模様、布目模様、皮絞模様、幾何学図形、文字、記号、抽象模様、草花模様等が挙げられ、目的に応じて選択できる。 The design pattern layer imparts design properties to the laminated sheet and the foamed laminated sheet. Examples of the design pattern include a grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, an abstract pattern, a flower pattern, etc. You can choose according to your purpose.
　絵柄模様層は、例えば、絵柄模様を印刷することで形成できる。印刷手法としては、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、オフセット印刷等が挙げられる。印刷インキとしては、着色剤、結着材樹脂、溶剤を含む印刷インキが使用できる。これらのインキは公知又は市販のものを使用してもよい。 The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent can be used. These inks may be known or commercially available.
　着色剤としては、例えば、前記の発泡剤含有樹脂層で使用されるような顔料を適宜使用することができる。 As the colorant, for example, a pigment used in the foaming agent-containing resin layer can be used as appropriate.
　結着材樹脂は、絵柄模様層を形成する下地の種類に応じて設定できる。例えば、アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、塩素化ポリオレフィン系樹脂、塩化ビニル－酢酸ビニル共重合体系樹脂、ポリビニルブチラール樹脂、アルキド系樹脂、石油系樹脂、ケトン樹脂、エポキシ系樹脂、メラミン系樹脂、フッ素系樹脂、シリコーン系樹脂、繊維素誘導体、ゴム系樹脂等が挙げられる。 The binder resin can be set according to the type of base on which the pattern layer is formed. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.
　溶剤（又は分散媒）としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の石油系有機溶剤；酢酸エチル、酢酸ブチル、酢酸－2－メトキシエチル、酢酸－2－エトキシエチル等のエステル系有機溶剤；メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、イソブチルアルコール、エチレングリコール、プロピレングリコール等のアルコール系有機溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤；ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤；ジクロロメタン、四塩化炭素、トリクロロエチレン、テトラクロロエチレン等の塩素系有機溶剤；水などが挙げられる。これらの溶剤（又は分散媒）は、単独又は混合物の状態で使用できる。 Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Chlorinated organic solvents; and water. These solvents (or dispersion media) can be used alone or in the form of a mixture.
　絵柄模様層の厚みは、絵柄模様の種類より異なるが、一般には0.1～10μm程度とすることが好ましい。 The thickness of the pattern layer varies depending on the type of pattern, but is generally preferably about 0.1 to 10 μm.
　プライマー層
　樹脂層（発泡剤含有樹脂層、非発泡樹脂層A等）又は絵柄模様層の上には、必要に応じてプライマー層を形成してもよい。 A primer layer may be formed as necessary on the primer layer resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.) or the pattern layer.
　プライマー層に含有される樹脂としては、例えば、アクリル、塩化ビニル－酢酸ビニル共重合体、ポリエステル、ポリウレタン、塩素化ポリプロピレン、塩素化ポリエチレン等を使用することができるが、特にアクリル、塩素化ポリプロピレン等が望ましい。 As the resin contained in the primer layer, for example, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used. Particularly, acrylic, chlorinated polypropylene, etc. Is desirable.
　アクリルとしては、例えば、ポリ（メタ）アクリル酸メチル、ポリ（メタ）アクリル酸エチル、ポリ（メタ）アクリル酸プロピル、ポリ（メタ）アクリル酸ブチル、（メタ）アクリル酸メチル－（メタ）アクリル酸ブチル共重合体、（メタ）アクリル酸エチル－（メタ）アクリル酸ブチル共重合体、エチレン－（メタ）アクリル酸メチル共重合体、スチレン－（メタ）アクリル酸メチル共重合体等の（メタ）アクリル酸エステルを含む単独又は共重合体からなるアクリル樹脂が挙げられる。 Examples of the acryl include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylate methyl- (meth) acrylic acid (Meth) such as butyl copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester may be mentioned.
　ポリウレタンとはポリオール（多価アルコール）を主剤とし、イソシアネートを架橋剤（硬化剤）とする組成物である。 Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).
　ポリオールとしては、分子中に2個以上の水酸基を有するもので、例えば、ポリエチレングリコール、ポリプロピレングリコール、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール等が用いられる。 As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.
　また、イソシアネートとしては、分子中に2個以上のイソシアネート基を有する多価イソシアネートが用いられる。例えば、2－4トリレンジイソシアネート、キシレンジイソシアネート、4－4ジフェニルメタンジイソシアネート等の芳香族イソシアネート、或いはヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等の脂肪族（又は脂環族）イソシアネートが用いられる。 As the isocyanate, polyisocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate ) Isocyanates are used.
　プライマー層の厚さは限定的ではないが、0.1～10μm程度が好ましく、0.1～5μm程度がより好ましい。 The thickness of the primer layer is not limited, but is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm.
　表面保護層
　樹脂層（発泡剤含有樹脂層、非発泡樹脂層A等）、絵柄模様層又はプライマー層の表面には艶調整及び／又は絵柄模様層の保護を意図して表面保護層を有してもよい。 Surface protective layer Resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.), pattern layer or primer layer has a surface protective layer intended for gloss adjustment and / or pattern layer protection May be.
　表面保護層の種類は限定的ではない。艶調整を目的とする表面保護層であれば、例えば、シリカなどの既知フィラーを含む表面保護層がある。表面保護層の形成方法としては、グラビア印刷などの公知の方法が採用できる。 The type of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed.
　積層シートの表面強度（耐スクラッチ性など）、耐汚染性、絵柄模様層の保護等を目的として表面保護層を形成する場合には、電離放射線硬化型樹脂を樹脂成分として含有するものが好適である。電離放射線硬化型樹脂としては、電子線照射によってラジカル重合（硬化）するものが好ましい。 When a surface protective layer is formed for the purpose of surface strength (scratch resistance, etc.), contamination resistance, pattern layer protection, etc. of laminated sheets, those containing ionizing radiation curable resins as resin components are suitable. is there. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.
　エンボス
　積層シート又は発泡積層シートのおもて面にはエンボス模様を付してもよい。この場合、最表面層（繊維質シートと反対側）の上からエンボス加工すれば良い。エンボス加工は、エンボス版の押圧等、公知の手段により実施することができる。例えば、最表面層が表面保護層である場合は、そのおもて面を加熱軟化後、エンボス版を押圧することにより所望のエンボス模様を賦型できる。エンボス模様としては、例えば木目板導管溝、石板表面凹凸、布表面テクスチャア、梨地、砂目、ヘアライン、幾何学模様、万線条溝、輪郭模様等がある。 An embossed pattern may be provided on the front surface of the embossed laminated sheet or the foamed laminated sheet. In this case, what is necessary is just to emboss from the uppermost surface layer (opposite side to the fibrous sheet). Embossing can be performed by known means such as pressing an embossed plate. For example, when the outermost surface layer is a surface protective layer, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a sand texture, a hairline, a geometric pattern, a multi-row groove, and a contour pattern.
　≪発泡積層シート≫
　本発明の発泡積層シートは、上記積層シートの発泡剤含有樹脂層を発泡させることにより得られる。 ≪Foamed laminated sheet≫
The foamed laminated sheet of the present invention can be obtained by foaming the foaming agent-containing resin layer of the laminated sheet.
　≪積層シート及び発泡積層シートの製造方法≫
　本発明の積層シートの製造方法は限定的ではないが、例えば、
（1）繊維質基材上に少なくとも樹脂層を形成する工程と、
（2）前記繊維質基材に電離放射線架橋型材料を含浸する工程と、を有し、
　上記2つの工程を経た後に、少なくとも前記繊維質基材に電離放射線を照射し、前記電離放射線架橋型材料を架橋させることにより架橋物を形成することを特徴とする製造方法によって製造することができる。 ≪Laminated sheet and foamed laminated sheet manufacturing method≫
Although the manufacturing method of the laminated sheet of the present invention is not limited, for example,
(1) forming at least a resin layer on the fibrous base material;
(2) impregnating the fibrous base material with an ionizing radiation cross-linking material,
After passing through the above-mentioned two steps, at least the fibrous base material is irradiated with ionizing radiation, and the ionized radiation cross-linking material is cross-linked to form a cross-linked product. .
　即ち、上記製造方法においては、繊維質基材（架橋物を含有するものと繊維質シートの状態であるものとの両方を含む）に樹脂層を形成する工程と、繊維質基材（架橋物を含有しないもの）に電離放射線架橋型材料を含浸する工程と、を有し、当該2つの工程を経た後に、少なくとも前記繊維質基材に電離放射線を照射し、前記電離放射線架橋型材料を架橋させることにより架橋物を形成する。ここで、樹脂層は押出し製膜によって形成することが好ましい。 That is, in the above production method, a step of forming a resin layer on a fibrous base material (including both a crosslinked material and a fibrous sheet), and a fibrous substrate (crosslinked material) And the step of impregnating the ionizing radiation cross-linkable material with the ionizing radiation cross-linking material after passing through the two steps and at least irradiating the fibrous base material with ionizing radiation. To form a cross-linked product. Here, the resin layer is preferably formed by extrusion film formation.
　上記製造方法においては、（1）と（2）の工程を行う順序は限定されないが、樹脂層を押出し製膜によって形成する場合には、繊維質基材上に樹脂層を密着性良く積層する観点からは、（1）の工程を行った後に（2）の工程を行うことが好ましい。 In the above production method, the order of performing the steps (1) and (2) is not limited, but when the resin layer is formed by extrusion film formation, the resin layer is laminated on the fibrous base material with good adhesion. From the viewpoint, it is preferable to perform the step (2) after performing the step (1).
　樹脂層を押出し製膜により形成して繊維質基材上に積層する際に繊維質基材として合成繊維混抄紙や不織布を用いる場合には、繊維質基材と樹脂層とを密着性よく積層することが困難となるおそれがある。一方、本発明の積層シート及びその製造方法によれば、合成繊維混抄紙や不織布以外の、樹脂層との密着性が良好な繊維質基材を用いた場合においても、被施工面に接着剤を塗工した後での施工や、貼り替えの際の繊維質基材と接着剤との間での剥離が可能となるため、繊維質基材と樹脂層との密着性と、施工及び貼り替えの容易性との両立を図ることができる。 When synthetic resin mixed paper or nonwoven fabric is used as the fibrous base material when the resin layer is formed by extrusion film formation and laminated on the fibrous base material, the fibrous base material and the resin layer are laminated with good adhesion. May be difficult to do. On the other hand, according to the laminated sheet of the present invention and the method for producing the same, an adhesive is applied to the work surface even when a fibrous base material having good adhesion to the resin layer other than the synthetic fiber mixed paper or nonwoven fabric is used. Since it is possible to peel off between the fibrous base material and the adhesive during the application or coating, the adhesion between the fibrous base material and the resin layer, construction and pasting Compatibility with ease of replacement can be achieved.
　（2）の工程において繊維質基材に電離放射線架橋型材料を含浸する方法としては、特に限定されないが、繊維質基材上（（1）の工程を先に行った場合は樹脂層が形成された面の反対側）に電離放射線架橋型材料を塗工する方法、繊維質基材を電離放射線架橋型材料に浸漬する方法等が挙げられる。電離放射線架橋型材料は、必要に応じて溶剤によって希釈して用いてもよい。 The method of impregnating the fibrous base material with the ionizing radiation cross-linking material in the step (2) is not particularly limited, but the resin layer is formed on the fibrous base material (if the step (1) is performed first) For example, a method of coating the ionizing radiation crosslinkable material on the opposite side of the formed surface, a method of immersing the fibrous base material in the ionizing radiation crosslinkable material, and the like. The ionizing radiation cross-linking material may be diluted with a solvent as necessary.
　樹脂層が発泡剤含有樹脂層を含む積層体からなる層であって、当該発泡剤含有樹脂層の片面又は両面に非発泡樹脂層を有する場合には、非発泡樹脂層B及び／又は非発泡樹脂層Aを、押出し製膜により形成してもよいし、各フィルムを熱ラミネートすることにより形成してもよいが、Tダイ押出し機による同時押出し製膜が好適である。例えば、両面に非発泡樹脂層を有する場合には、3つの層に対応する溶融樹脂を同時に押出すことにより3層の同時成膜が可能なマルチマニホールドタイプのTダイを用いることができる。 When the resin layer is a layer composed of a laminate including a foaming agent-containing resin layer and has a non-foaming resin layer on one or both sides of the foaming agent-containing resin layer, the non-foaming resin layer B and / or non-foaming The resin layer A may be formed by extrusion film formation or may be formed by heat laminating each film, but simultaneous extrusion film formation by a T-die extruder is suitable. For example, in the case of having non-foamed resin layers on both sides, a multi-manifold type T die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers can be used.
　なお、発泡剤含有樹脂層を形成する樹脂組成物に無機充填剤が含まれる場合であって、発泡剤含有樹脂層を押出し製膜により形成する場合には、押出し機の押出し口（いわゆるダイス）に無機充填剤の残渣（いわゆる目やに）が発生し易く、これが発泡剤含有樹脂層表面の異物となり易い。そのため、発泡剤含有樹脂層を形成する樹脂組成物に無機充填剤が含まれる場合には、上記のように3層同時押出し製膜することが好ましい。即ち、発泡剤含有樹脂層を非発泡樹脂層によって挟み込んだ態様で同時押出し製膜することにより、前記目やにの発生を抑制することができる。 In addition, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer and the foaming agent-containing resin layer is formed by extrusion film formation, an extrusion port (so-called die) of the extruder is used. Inorganic filler residues (so-called eyes and eyes) are easily generated, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic filler is included in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above. That is, it is possible to suppress the occurrence of the above-mentioned corners by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers.
　発泡剤含有樹脂層を製膜後は、電子線照射を行ってもよい。これにより樹脂成分を架橋して発泡樹脂層の表面強度、発泡特性等を調整することができる。電子線のエネルギーは、150～250kV程度が好ましく、175～200kV程度がより好ましい。照射量は、10～100kGy程度が好ましく、10～50kGy程度がより好ましい。電子線源としては、公知の電子線照射装置が使用できる。なお、特に繊維質基材に照射する電離放射線が電子線である場合には、電離放射線架橋型材料の架橋と上記発泡剤含有樹脂層の樹脂架橋とを同時に行うこともできる。 After forming the foaming agent-containing resin layer, electron beam irradiation may be performed. Thereby, the resin component can be cross-linked to adjust the surface strength, foaming characteristics, etc. of the foamed resin layer. The energy of the electron beam is preferably about 150 to 250 kV, more preferably about 175 to 200 kV. The irradiation dose is preferably about 10 to 100 kGy, more preferably about 10 to 50 kGy. A known electron beam irradiation apparatus can be used as the electron beam source. In particular, when the ionizing radiation applied to the fibrous base material is an electron beam, crosslinking of the ionizing radiation crosslinking material and resin crosslinking of the foaming agent-containing resin layer can be performed simultaneously.
　発泡剤含有樹脂層上には、必要に応じて、絵柄模様層及びプライマー層を任意の順序で形成した後、必要に応じて、表面保護層を形成して積層シートとし、次に熱処理して発泡剤含有樹脂層を発泡樹脂層にすることで発泡積層シートが得られる。図1に、繊維質基材上に、非発泡樹脂層B、発泡剤含有樹脂層、非発泡樹脂層A、絵柄模様層、プライマー層及び表面保護層を順に形成した積層シートの層構成を例示する。これらの各層は、印刷、塗布などのコーティング、押出し製膜等を組み合わせることにより積層でき、印刷、塗布等のコーティングは常法に従って行うことができる。 On the foaming agent-containing resin layer, if necessary, a pattern layer and a primer layer are formed in any order, and if necessary, a surface protective layer is formed to form a laminated sheet, and then heat-treated. A foaming laminated sheet is obtained by making the foaming agent-containing resin layer into a foamed resin layer. Fig. 1 illustrates the layer structure of a laminated sheet in which a non-foamed resin layer B, a foaming agent-containing resin layer, a non-foamed resin layer A, a pattern pattern layer, a primer layer, and a surface protective layer are sequentially formed on a fibrous base material. To do. Each of these layers can be laminated by combining coating such as printing and coating, extrusion film formation and the like, and coating such as printing and coating can be performed according to a conventional method.
　熱処理条件は、熱分解型発泡剤の分解により発泡樹脂層が形成される条件であればよく、加熱温度は210～240℃程度が好ましく、加熱時間は25～80秒程度が好ましい。また、エンボス模様を付す場合には、エンボス版の押圧等、公知の手段により実施する。 The heat treatment conditions may be any conditions as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 25 to 80 seconds. Further, when an embossed pattern is added, it is carried out by a known means such as pressing an embossed plate.
　≪積層シート及び発泡積層シートの施工方法≫
　本発明の積層シート及び発泡積層シートは、前述の通り、被施工面に接着剤を塗工した後、当該被施工面に貼着することで施工することができる。本発明の積層シート及び発泡積層シートが適用される被施工面としては特に限定されず、装飾が要求される各種の用途が適用でき、被施工面として壁面及び／又は天井が好適に挙げられる。即ち、本発明の積層シート及び発泡積層シートは、壁紙及び／又は天井材として特に有用である。 ≪Construction method of laminated sheet and foam laminated sheet≫
As described above, the laminated sheet and the foamed laminated sheet of the present invention can be constructed by applying an adhesive to the construction surface and then sticking it to the construction surface. The construction surface to which the laminated sheet and the foamed laminated sheet of the present invention are applied is not particularly limited, and various uses that require decoration can be applied, and examples of the construction surface include a wall surface and / or a ceiling. That is, the laminated sheet and the foamed laminated sheet of the present invention are particularly useful as wallpaper and / or ceiling material.
　本発明の積層シート及び発泡積層シートの施工に用いる接着剤としては特に限定されず、デンプン系接着剤（デンプン糊、デンプン糊に合成樹脂を添加したもの等）、メチルセルロース系接着剤などの慣用の接着剤を、被施工面の種類に応じて選択して使用することができる。前述の通り、本発明の積層シート及び発泡積層シートは、メチルセルロース系接着剤以外の接着剤、例えば、壁紙及び天井材の施工において一般的に用いられるデンプン系接着剤を用いて施工した場合でも、貼り替え時に繊維質基材と接着剤との間で剥離することが可能であり、被施工面に繊維質基材が残り難く、貼り替えが容易である。 The adhesive used for the construction of the laminated sheet and the foamed laminated sheet of the present invention is not particularly limited, and conventional adhesives such as starch adhesives (starch glue, starch paste with a synthetic resin added, etc.), methylcellulose adhesives, etc. The adhesive can be selected and used according to the type of the work surface. As described above, the laminated sheet and the foamed laminated sheet of the present invention are adhesives other than methylcellulose-based adhesives, for example, when applied using a starch-based adhesive generally used in the construction of wallpaper and ceiling materials, It is possible to peel between the fibrous base material and the adhesive at the time of replacement, and it is difficult for the fibrous base material to remain on the work surface, so that replacement is easy.
　なお、本発明の積層シート及び発泡積層シートの施工方法は、上記の施工方法に限定されず、積層シート及び発泡積層シートの裏側（繊維質基材の裏側）に接着剤を塗工後、被施工面に貼着する、一般的な方法により施工することも可能である。 In addition, the construction method of the laminated sheet and the foamed laminated sheet of the present invention is not limited to the construction method described above, and after applying the adhesive to the back side of the laminated sheet and the foamed laminated sheet (the back side of the fibrous base material), It is also possible to construct by a general method of sticking to the construction surface.
　以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
　実施例1
　3種3層マルチマニホールドTダイ押出し機を用い、i)非発泡樹脂層B、ii)発泡剤含有樹脂層及びiii)非発泡樹脂層Aの順に、厚み7μm、70μm及び7μmになるように製膜した。押し出し条件は、前記i)層の樹脂はシリンダー温度100℃とし、前記ii)層の樹脂組成物はシリンダー温度120℃とし、前記iii)層の樹脂はシリンダー温度130℃とした。ダイス温度は全て120℃とした。 Example 1
Using a three-type, three-layer multi-manifold T-die extruder, i) non-foamed resin layer B, ii) foaming agent-containing resin layer, and iii) non-foamed resin layer A in this order were 7 μm, 70 μm, and 7 μm thick. Filmed. The extrusion conditions were as follows: the i) layer resin had a cylinder temperature of 100 ° C., the ii) layer resin composition had a cylinder temperature of 120 ° C., and the iii) layer resin had a cylinder temperature of 130 ° C. The die temperatures were all 120 ° C.
　製膜後、表面温度を120℃に加熱した普通紙裏打紙（WK-665DO、KJ特殊紙製）に、前記i)層の面を積層し、積層直後に電離放射線架橋型材料「NKエステル ADCP、新中村化学製」を裏打紙側から塗工により含浸させた。 After film formation, the surface of i) layer is laminated on plain paper backing paper (WK-665DO, KJ special paper) heated to a surface temperature of 120 ° C. "Shin Nakamura Chemical" was impregnated by coating from the backing paper side.
　次に、前記iii)層上から電子線（200KV、30kGy）を照射して、含浸させた電離放射線架橋型材料を架橋するとともに、少なくとも発泡剤含有樹脂層ii)を樹脂架橋させて積層シートを作製した。 Next, the above iii) layer is irradiated with an electron beam (200 KV, 30 kGy) to crosslink the impregnated ionizing radiation cross-linked material, and at least the foaming agent-containing resin layer ii) is cross-linked to form a laminated sheet. Produced.
　次に、iii)層上にコロナ放電処理を行った。 Next, a corona discharge treatment was performed on the iii) layer.
　次に、グラビア印刷機によりプライマー処理としてEVA系水性エマルションを2g/m2コートし、その上に絵柄用水性インキ（「ハイドリック」、大日精化工業株式会社製）、保護層用水性インキ（「ALTOP」、大日精化工業製）を用いて、グラビア印刷機により布目模様を印刷して絵柄模様層を形成後、連続して保護層を形成した。これにより、繊維質基材層（普通紙裏打紙）、非発泡樹脂層B、発泡剤含有樹脂層、非発泡樹脂層A、プライマー層、絵柄模様層及び保護層を順に有する積層シート（未発泡原反）を得た。 Then, the EVA-based aqueous emulsion was 2 g / m 2 coating as a primer treatment by a gravure printing machine, thereon picture water based ink ( "Hyde Rick" Dainichiseika Color & Chemicals Mfg. Co., Ltd.), the protective layer water based ink ( Using “ALTOP” (manufactured by Dainichi Seika Kogyo Co., Ltd.), a texture pattern was printed by a gravure printing machine to form a pattern layer, and then a protective layer was formed. Thereby, a laminated sheet (non-foamed) having a fibrous base material layer (plain paper backing paper), a non-foamed resin layer B, a foaming agent-containing resin layer, a non-foamed resin layer A, a primer layer, a pattern layer and a protective layer in this order. The original fabric was obtained.
　次に、ギアオーブンにて加熱（220℃×30秒）し、発泡剤含有樹脂層に含まれる発泡剤を発泡させた。更に、発泡体に対して最表面から布目パターン凹凸エンボスを施し、発泡積層シート（発泡壁紙）を作製した。 Next, the foaming agent contained in the foaming agent-containing resin layer was foamed by heating in a gear oven (220 ° C. × 30 seconds). Furthermore, the embossed texture pattern was applied to the foam from the outermost surface to prepare a foamed laminated sheet (foamed wallpaper).
　各層は、それぞれ以下の成分を用いて形成した。
i)非発泡樹脂層Bは、EVA「エバフレックスEV150（VA含有量＝33重量％）、三井・デュポン ポリケミカル製」により形成した。
ii)発泡剤含有樹脂層は、EVA「エバテートH4011（VA含有量＝20重量％）、住友化学製」100重量部、炭酸カルシウム「ホワイトンH、東洋ファインケミカル製」30重量部、二酸化チタン「CR-63、石原産業製」25重量部、発泡剤「ビニホールAC#3、永和化成工業製」4重量部、発泡助剤「エフコ・ケムZNS-P ADEKA製」4重量部、架橋助剤「オプスターJUA-702、JSR製」1重量部を含む樹脂組成物により形成した。
iii)非発泡樹脂層Aは、エチレン－メタクリル酸共重合体樹脂「ニュクレルN1560、三井・デュポン ポリケミカル製」により形成した。 Each layer was formed using the following components.
i) The non-foamed resin layer B was formed by EVA “Evaflex EV150 (VA content = 33 wt%), manufactured by Mitsui DuPont Polychemical”.
ii) The foaming agent-containing resin layer consists of EVA "Evaate H4011 (VA content = 20% by weight), Sumitomo Chemical" 100 parts by weight, calcium carbonate "Whiteon H, Toyo Fine Chemical" 30 parts by weight, titanium dioxide "CR -63, manufactured by Ishihara Sangyo Co., Ltd. ”25 parts by weight, foaming agent“ Vinihole AC # 3, manufactured by Eiwa Kasei Kogyo ”4 parts by weight, foaming aid“ Fco Chem ZNS-P ADEKA ”4 parts by weight, crosslinking aid“ OPSTAR ” "JUA-702, made by JSR" was formed from a resin composition containing 1 part by weight.
iii) The non-foamed resin layer A was formed from an ethylene-methacrylic acid copolymer resin “Nucleel N1560, manufactured by Mitsui DuPont Polychemical”.
　比較例1
　裏打紙に電離放射線架橋型材料を含浸させない以外は、実施例1と同様にして積層シート及び発泡積層シートを作製した。 Comparative Example 1
A laminated sheet and a foamed laminated sheet were produced in the same manner as in Example 1 except that the backing paper was not impregnated with the ionizing radiation cross-linking material.
　比較例2
　裏打紙としてパルプと合成繊維を混抄したフリース紙（アールストローム製）を用い、且つ、裏打紙に電離放射線架橋型材料を含浸させない以外は、実施例1と同様にして積層シート及び発泡積層シートを作製した。 Comparative Example 2
A laminated sheet and a foamed laminated sheet were prepared in the same manner as in Example 1 except that fleece paper (made by Ahlstrom), which was a mixture of pulp and synthetic fiber, was used as the backing paper and the backing paper was not impregnated with ionizing radiation cross-linking material. Produced.
　試験例1
　樹脂層と裏打紙との密着性を、発泡積層シートの樹脂層を裏打紙から巾方向で剥がすことにより評価した。評価基準は次の通りである。
○：樹脂層が全巾にわたり裏打紙の繊維を持ってくる。
△：樹脂層が部分的に裏打紙の繊維を持ってくる。
×：樹脂層が全く裏打紙の繊維を持ってこない。 Test example 1
The adhesion between the resin layer and the backing paper was evaluated by peeling the resin layer of the foamed laminated sheet from the backing paper in the width direction. The evaluation criteria are as follows.
○: The resin layer brings the fiber of the backing paper over the entire width.
Δ: The resin layer partially brings the backing paper fibers.
X: The resin layer does not bring the fiber of the backing paper at all.
　試験例2
　発泡積層シートの水中伸度を評価した。具体的には、発泡積層シートをMD方向5cm、TD方向11cmの寸法にカットし、MD方向の中央からTD方向の巾なりになるように10cm長の標線を引き、水中に1時間浸漬し、浸漬前後の標線長差より変化率を求めた。水中伸度の評価基準は次の通りである。
○：0.6％未満である
×：0.6％以上である。 Test example 2
The underwater elongation of the foamed laminated sheet was evaluated. Specifically, the foamed laminated sheet is cut into dimensions of 5 cm in the MD direction and 11 cm in the TD direction, a 10 cm long marked line is drawn from the center of the MD direction to the width in the TD direction, and immersed in water for 1 hour. The rate of change was determined from the difference in the marked line length before and after immersion. The evaluation criteria for elongation in water are as follows.
○: Less than 0.6% ×: 0.6% or more.
　試験例3
　石膏ボード面に（1）メチルセルロース系接着剤（メチランスペシャル ヘンケル製）、（2）デンプン系接着剤（デンプン＋合成樹脂）（ルーアマイルド ヤヨイ化学工業製）を予め所定量を水に溶解させて接着剤として調製したものを塗工し、その上に各発泡積層シートの裏打紙面を貼り合せてから乾燥させて試験体とした。試験体に25mm巾の切り込みを入れて手で剥がして剥し面を観察した。評価基準は次の通りである。
○：裏打紙がボード面に残ることなく裏打紙、接着剤間で剥離する。
△：裏打紙が部分的に接着剤側に取られる。剥離が重い。
×※１：裏打紙が紙間で剥離して石膏ボード下地側に残る。
×※２：石膏ボード下地が剥がれる。 Test example 3
A predetermined amount of (1) methylcellulose adhesive (Methylan Special Henkel) and (2) starch adhesive (starch + synthetic resin) (made by Rua Mild Yayoi Chemical) are dissolved in water on the gypsum board surface. What was prepared as an adhesive agent was applied, and the backing paper surface of each foamed laminated sheet was laminated thereon and dried to obtain a test specimen. A 25 mm wide cut was made into the test piece and peeled off by hand, and the peeled surface was observed. The evaluation criteria are as follows.
○: The backing paper is peeled off between the backing paper and the adhesive without remaining on the board surface.
Δ: The backing paper is partially taken to the adhesive side. Heavy peeling.
× * 1 : The backing paper peels off between the papers and remains on the base of the gypsum board.
× * 2 : The gypsum board substrate peels off.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
1. 繊維質基材
2. 非発泡樹脂層B
3. 発泡剤含有樹脂層
4. 非発泡樹脂層A
5. 絵柄模様層
6. プライマー層
7. 表面保護層 1. Fibrous substrate
2. Non-foamed resin layer B
3. Foaming agent-containing resin layer
4. Non-foamed resin layer A
5. Pattern pattern layer
6. Primer layer
7. Surface protective layer

Claims (13)

  1. 　繊維質基材上に少なくとも樹脂層が積層されている積層シートであって、前記繊維質基材は電離放射線架橋型材料の架橋物を含有することを特徴とする積層シート。 A laminated sheet in which at least a resin layer is laminated on a fibrous base material, wherein the fibrous base material contains a cross-linked product of an ionizing radiation cross-linking material.
  2. 　前記樹脂層がオレフィン系樹脂層である、請求項1に記載の積層シート。 2. The laminated sheet according to claim 1, wherein the resin layer is an olefin resin layer.
  3. 　前記樹脂層が発泡剤含有樹脂層である、又は発泡剤含有樹脂層を含む積層体からなる層である、請求項1又は2に記載の積層シート。 3. The laminated sheet according to claim 1 or 2, wherein the resin layer is a foaming agent-containing resin layer or a layer comprising a laminate including the foaming agent-containing resin layer.
  4. 　前記発泡剤含有樹脂層は、片面又は両面に非発泡樹脂層を有する、請求項3に記載の積層シート。 4. The laminated sheet according to claim 3, wherein the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides.
  5. 　前記発泡剤含有樹脂層は、電子線照射により樹脂架橋されている、請求項3又は4に記載の積層シート。 5. The laminated sheet according to claim 3 or 4, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.
  6. 　請求項3～5のいずれかに記載の積層シートの発泡剤含有樹脂層を発泡させることにより得られる発泡積層シート。 A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of claims 3 to 5.
  7. 　（1）繊維質基材上に少なくとも樹脂層を形成する工程と、
    　（2）前記繊維質基材に電離放射線架橋型材料を含浸する工程と、を有し、
    　上記2つの工程を経た後に、少なくとも前記繊維質基材に電離放射線を照射し、前記電離放射線架橋型材料を架橋させることにより架橋物を形成することを特徴とする積層シートの製造方法。     (1) forming at least a resin layer on the fibrous base material;
    (2) impregnating the fibrous base material with an ionizing radiation cross-linking material,
    A method for producing a laminated sheet, wherein a cross-linked product is formed by irradiating at least the fibrous base material with ionizing radiation and cross-linking the ionizing radiation cross-linking material after passing through the two steps.
  8. 　前記繊維質基材上に少なくとも前記樹脂層を押出し製膜により形成する、請求項7に記載の積層シートの製造方法。 8. The method for producing a laminated sheet according to claim 7, wherein at least the resin layer is formed on the fibrous base material by extrusion film formation.
  9. 　前記樹脂層が発泡剤含有樹脂層である、又は発泡剤含有樹脂層を含む積層体からなる層であり、且つ、前記電離放射線が電子線であり、前記電子線の照射により、前記電離放射線架橋型材料の架橋と前記発泡剤含有樹脂層の樹脂架橋とを同時に行う、請求項7又は8に記載の積層シートの製造方法。 The resin layer is a foaming agent-containing resin layer, or a layer comprising a laminate including a foaming agent-containing resin layer, and the ionizing radiation is an electron beam, and the ionizing radiation crosslinking is performed by irradiation with the electron beam. 9. The method for producing a laminated sheet according to claim 7, wherein crosslinking of the mold material and resin crosslinking of the foaming agent-containing resin layer are performed simultaneously.
  10. 　前記樹脂層が発泡剤含有樹脂層である、又は発泡剤含有樹脂層を含む積層体からなる層である、請求項7～9のいずれかに記載の製造方法により製造される積層シートの前記発泡剤含有樹脂層を加熱により発泡させる発泡積層シートの製造方法。 The foamed laminate sheet produced by the production method according to any one of claims 7 to 9, wherein the resin layer is a foaming agent-containing resin layer or a layer comprising a laminate including the foaming agent-containing resin layer. The manufacturing method of the foaming lamination sheet which foams an agent containing resin layer by heating.
  11. 　接着剤を塗工した被施工面に請求項1～6のいずれかに記載の積層シート又は発泡積層シートを貼着することを特徴とする施工方法。 7. A construction method characterized in that the laminated sheet or the foamed laminated sheet according to any one of claims 1 to 6 is adhered to a work surface coated with an adhesive.
  12. 　請求項1～6のいずれかに記載の積層シート又は発泡積層シートの裏側に接着剤を塗工後、被施工面に貼着することを特徴とする施工方法。 A construction method comprising applying an adhesive to the back side of the laminated sheet or the foamed laminated sheet according to any one of claims 1 to 6 and then attaching the adhesive to a construction surface.
  13. 　前記被施工面は、壁面及び／又は天井である、請求項11又は12に記載の施工方法。 The construction method according to claim 11 or 12, wherein the construction surface is a wall surface and / or a ceiling.
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JPS6254674B2 (en) * 1978-11-30 1987-11-16 Toppan Printing Co Ltd
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JP2002001749A (en) * 2000-06-20 2002-01-08 Dainippon Printing Co Ltd Method for manufacturing decorative board
JP2006341472A (en) * 2005-06-08 2006-12-21 Daiken Trade & Ind Co Ltd Method for producing decorative panel
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WO2014051047A1 (en) * 2012-09-27 2014-04-03 大日本印刷株式会社 Laminate sheet and foamed laminate sheet

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